{"paper_id":"498cea1d-c1bd-4eab-8956-ea9788c836b0","body_text":"O2-Triggered Electrochemical Generation of Acyl Chloride Promoting Cascade Reaction of Esters Synthesis | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article O 2 -Triggered Electrochemical Generation of Acyl Chloride Promoting Cascade Reaction of Esters Synthesis Huajun Zheng, Zhefei Zhao, Linlin Zhang, Minhao Chen, Ruopeng Yu, and 9 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5948207/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 31 Jul, 2025 Read the published version in Journal of the American Chemical Society → Version 1 posted You are reading this latest preprint version Abstract Ester compounds as one of the most important organic chemicals are extensively used in chemical industry, medicines, food, plastics, cosmetics and other applications. Traditional ester synthesis is impeded by challenges of slow reaction kinetics, harsh conditions, and environmental concerns. Here, we propose a green and efficient route for synthesis of esters via an electrochemical dechlorination-oxygen insertion cascaded with chemical nucleophilic reaction. A high selectivity of 93.2%, and a yield of 92.5% for methyl 6-chloronicotinate (MCN) generation are obtained by electrochemical reduction of 2-chloro-5-trichloromethyl pyridine over the activated Ag electrode in an O 2 -saturated alcoholic solution. Electrochemical in-situ characterizations, femtosecond transient absorption spectra, isotope labeling, and theoretical calculations elucidate that the formation of intermediate acyl chloride is a key step, which involves reactive oxygen species of oxygen reduction reaction (ORR) coupling with dechlorination intermediate. The involvement of O₂ alters the electrochemical reaction pathway from conventional hydrodechlorination to oxygenation-dechlorination process, which is attributed to the preferentially occurred ORR than hydrogen evolution reaction. The generated acyl chloride further facilitates the subsequent chemical reaction in an alcoholic solution for MCN synthesis. The broad substrate scope and excellent performance in a flow electrolyzer validate the scalability and potential of this electrocatalysis-cascaded chemistry system for sustainable industrial production. Physical sciences/Chemistry/Electrochemistry/Electrocatalysis Physical sciences/Chemistry/Green chemistry Electrocatalytic Esters Synthesis Oxygen Reduction Reaction Dechlorination Cascade reaction Acyl chloride Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Introduction Esters compounds as one of the most versatile and widely produced organic chemicals in industry, are widely used for lubricants 1 , emulsifiers 2 , dispersants 3 , industrial solvents 4 , cosmetic additives 5 , pharmaceutical intermediates 6 , food flavors 7 , pesticides 8 , plastics 9 , etc. Motivated by the accelerating market demand, the global market for esters is projected to reach US $ 27.8 billion by 2029, growing at a compound annual rate (CAGR) of 6.4% from 2022 to 2029 10 . Currently, industrial production of esters predominantly relies on thermocatalytic strategy 11 , 12 . The traditional esterification reaction is a well-established pathway due to its simplicity and wide applicability (Fig. 1 a) 13 , 14 . However, this approach typically requires excessive reactants and operates under harsh conditions, such as the use of concentrated sulfuric acid, under elevated temperatures, and high pressures, leading to organic carbonization, poor product selectivity, and severe equipment corrosion, as well as intensive energy input and environmental concerns 15 , 16 . To address these limitations, the acyl chloride esterification method was developed, involving transformation of organic acids to intermediate acyl chlorides and the subsequent nucleophilic reaction (Fig. 1 b) 17 . Generation of acyl chloride significantly enhance the reactivity of the subsequent nucleophilic reaction, enabling higher productivity and simpler ester separation 18 . Despite these advantages, the use of acylating agents such as thionyl chloride (SOCl₂) 19 , oxalyl chloride (C₂O₂Cl₂) 20 , phosgene (COCl₂) 21 , and phosphorus trichloride (PCl₃) 22 introduces additional complexity. These additives can produce harmful gases and further complicate the reaction process 23 . Clearly, the current thermocatalytic strategies in industrial ester production face significant challenges. To address these challenges, Yoshio Hisaeda and Hisashi Shimakoshi proposed a photocatalytic process for acyl chloride generation, utilizing the dechlorination of trichloromethyl compounds, thereby eliminating the need for acylating agents (Fig. 1 c) 24 , 25 . This innovative approach offers significant advantages for ester production, particularly by overcoming the detrimental aspects of traditional thermocatalytic methods. However, the industrial application of photocatalysis is still constrained by the low energy utilization efficiency, difficulties in catalyst separation, and slow reaction kinetics 26 , 27 . In recent years, electrocatalysis has emerged as a promising strategy for synthesizing value-added compounds due to its high reactivity, controllable selectivity, mild reaction conditions, environmental friendliness, and scalability (Fig. 1 d) 28 – 30 . However, acyl chloride synthesis from trichloromethyl compounds through the electrochemical method is challenging. The cathodic process of electrochemical reduction trichloromethyl compounds involves three types of reactions (dechlorination, hydrogenation, and oxygen reduction reaction (ORR)). Conventional path is prone to the coupling of progressive dechlorination and hydrogenation steps (i.e., hydrodechlorination, Path 1, Supplementary Figs. 1 ), typically resulting in a mixture of hydrodechlorination products 31 , 32 . Undoubtedly, the synthesis of acyl chloride requires switch from the hydrodechlorination process to the coupling of dechlorination and oxygenation ( Path 2, Supplementary Figs. 1 and note 1 ). How to obtain reactive oxygen species (ROSs) and prioritize oxygen insertion step has become crucial. Regrettably, to date, studies on the electrochemical method for acyl chloride synthesis remain sparse, let alone ascertaining the reaction mechanism and the influence factors of interlaced coupling of possible electrochemical reduction steps. Here, we propose an oxygen (O₂)-triggered electrochemical process for acyl chloride generation, followed by cascading with chemical nucleophilic reaction for the highly selective synthesis of esters (Fig. 1 d). Using 2-chloro-5-trichloromethyl pyridine (TCMP) as a model reaction substrate, under continuous O 2 supply in tetrabutylammonium tetrafluoroborate (TBAT) solution using CH 3 OH as solvent, the O₂ insertion behavior over the activated Ag electrode is achieved during the electrochemical process via ROSs of oxygen reduction reaction (ORR) coupling with dechlorination intermediate. The generation of ROSs is thermodynamically more favorable than active hydrogen production by hydrogen evolution reaction (HER), thereby shifting the reaction pathway from the conventional stepwise hydrodechlorination to the formation of 6-chloronicotinoyl chloride (CNC). As a result, superior performance for MCN synthesis was achieved with 93.2% of high selectivity, 92.5% of yield, and excellent cycling stability over the activated Ag electrode at the potential of − 0.6 V vs Ag/AgCl. Furthermore, the wide substrate scope and excellent performance in flow electrolyzer validate the broad and promising applicability of this electrocatalysis-cascaded chemistry system for esters synthesis. Results Design of reaction system The O 2 -triggered electrochemical-chemical nucleophilic reaction cascaded system is shown in Fig. 2 a. The electrocatalytic product, CNC will be obtained via the substrate TCMP reacted with O 2 over the activated Ag mesh (Ag (a) ) electrode, then quickly converted to MCN by chemical nucleophilic reaction. Both electrolytic synthesis of CNC and subsequent chemical nucleophilic reaction to generate MCN occur in the cathode chamber of the electrolytic cell. In detail, a continuous flow of O 2 is pumped into CH 3 OH solution containing TCMP as the substrate and TBAT as the electrolyte in the cathode electrolysis system. The purpose of using these solvents and electrolytes is forming the organic environment for electrolysis, which is more difficult to ionize than aqueous solution, resulting in minimize the occurrence of HER as much as possible. Of course, CH 3 OH not only acts as a solvent but also drives nucleophilic reactions towards a more favorable direction for synthesizing MCN. In fact, continuous O 2 supply is a very important step. The pumped O 2 as mainly oxygen source is first reduced to ROSs (i.e., O*) over the Ag (a) ) electrode, which can directly react with the dechlorinated intermediate of TCMP. The Ag (a) electrode is specifically chosen as the cathode because of its high activity for electrochemical dechlorination and ease of ORR reaction at low overpotential. The preparation of the Ag (a) electrode through the electrochemical cyclic voltammetry (CV) activation treatments has been reported in our previous research 33 , 34 . The crystallographic structures, microstructures, and chemical states were probed by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy (XPS) ( Supplementary Figs. 2–8, Tables 1–2, and notes 2–7 ). Compared to the Ag without activation, Ag (a) exhibits rougher surface with nanoscale clusters and lower valence state, resulting in larger active specific surface area and enhanced site activity for dechlorination 35 , 36 . O-triggered electrocatalytic dechlorination cascaded with chemical reaction Linear sweep voltammetry (LSV) was measured under different atmospheres with or without TCMP (Fig. 2 b). In an anaerobic environment (N 2 ), no significant current can be observed when TCMP is absent in solution (yellow dotted line). The increase of current with an onset potential of − 0.15 V after adding TCMP indicates the electrochemical reduction of TCMP (yellow solid line). Upon pumping of O 2 , the apparently increased current and positively shifted onset potential (0.07 V) can be seen (blue dotted line), suggesting that O 2 participates in the electrochemical reductive reaction (oxygen reduction reaction, ORR) with a low overpotential. Further, a higher current can be obtained after adding TCMP (blue solid line), implying simultaneous ORR and dechloridation. For further studying the behavior of increased current in O 2 involved reaction, a series of electrolytic experiments were conducted under various environments. TCMP and products (CCMP, CMP, MCN, CNA) were quantified by high-performance liquid chromatography (HPLC) according to the corresponding calibration curves ( Supplementary Fig. 9 ). DCMP was detected by liquid chromatography-mass spectrometry (LCMS) in Supplementary Fig. 10 . As shown in Fig. 2 c, in N 2 -saturated CH 3 OH solution using TBAT as an electrolyte, only hydrodechlorination products (5.2% of DCMP, 2.0% of CCMP, and 3.8% of CMP) of Path 1 can be detected. In contrast, in the situation of O 2 saturation, the majority of products (92.5% of MCN, and 3.0% of CNA) belong to the oxygenation-dechlorination products in Path 2 . Combined with the result in the mixed gas (O 2 /N 2 , 20/80) further confirms the decisive effect of O 2 for route switching ( Supplementary Fig. 11 and note 8 ). Meanwhile, the addition of O 2 distinctly improves the conversion (from 11.0–99.2% in CH 3 OH solution with TBAT). Additionally, this O 2 -switched phenomenon can be also seen when changing solvent (from CH 3 OH to CH 3 CN in Fig. 2 c) and electrolyte (from TBAT to LiOAc in Supplementary Fig. 12 and note 9 ). Assuredly, compared with solvent and electrolyte, the presence of O 2 plays a determining role in the choice of electrochemical pathways. Notably, solvent and electrolyte also have effect on the subsequent chemical reaction. As shown in Fig. 2 c, only CNA can be seen as the oxygenation-dechlorination product when using CH 3 CN as solvent in the presence of O 2 , verifying the subsequent chemical reaction for MCN formation using CH 3 OH as nucleophile. The source of CNA may be attributed to the inevitable H 2 O in the solution or produced by ORR, which is explained by a series of electrochemical measurements in Supplementary Fig. 13 and Note 10 . Further, the substrate and products over time under various electrolytic environments are shown in Supplementary Fig. 14 and note 11 . The effect of potential under different atmosphere conditions was further investigated (Fig. 2 d and Supplementary Fig. 15 ). In saturated-O 2 situation, the conversion of TCMP and yield of MCN present sharp growing trend with the increasing the cathodic potential from 0 to − 0.6 V, and then maintain the steady values from − 0.6 to − 1.4 V. The optimal conversion (99.2%) of TCMP and yield of MCN (92.5%) can be found at the potential of − 0.6 V. In saturated-N 2 situation, although an increase of TCMP conversion can be obtained with the increasing of potential (from 0 to − 1.4 V), the highest conversion is only 49.0% at − 1.4 V, showing the lower reactivity compared with the reaction in saturated-O 2 situation. Meanwhile, potential also affects the selectivity of dechlorination products, and the yield of CMP increases with potential increasing, which is owing to the acceleration of stepwise dechlorination ( Supplementary Table S3 ). In addition, the O 2 -participated reaction begins at an earlier potential (− 0.2 V) in contrast to that of hydrodechlorination process (− 0.4 V), indicating that this reaction is more favorable. The electrolysis result in the mixed gas (O 2 /N 2 , 20/80) environment shown in Supplementary Fig. 15 confirms that a more negative potential may promote the production of hydrodechlorination products in the case of insufficient O 2 , causing the competition of Path 1 . Potential-dependent Bode phase plots were employed to disclose the in-situ interfacial reaction properties (Fig. 2 e, Supplementary Fig. 16 ). Under the condition of without TCMP in N 2 , the peak at the low and medium frequency region begins to sharply decrease at − 0.8 V, indicating the occurrence of hydrogen evolution reaction (HER). After adding TCMP, the amplitude of the phase angle decreased, and the peak at − 0.2 V rapidly decreased, suggesting the start of TCMP reduction with fast charge transfer. Moreover, the negative shift of peak can be seen from − 0.6 to − 1.4 V, signifying the stepwise hydrodechlorination process. Without TCMP in O 2 -saturated atmosphere (Fig. 2 e), the distinct decrease of the phase angle amplitude at − 0.2 V suggesting the occurrence of ORR reaction, which is consistent with the LSV results. Obviously, a more negative potential is needed for HER (− 0.8 V) than ORR (− 0.2 V), demonstrating ORR is more likely to occur than HER. The above result explains the importance of the thermodynamically preferred ORR to the pathway switch. After adding TCMP ( Supplementary Fig. 13c ), the disappearance of the negatively shifted peak implies that the stepwise hydrodechlorination vanishes and is replaced by the ORR-coupled dechlorination process. The electrode-solution interface microenvironment, regulating by electrolyte, plays a vital role in selectivity of products. Hence, the influence of electrolytes (concentration and variety) on the selectivity of MCN was evaluated in O 2 -saturated CH 3 OH solution. The selectivity of MCN increases with the decrease of electrolyte concentration, and the degree of this trend is dominated by electrolyte variety (Fig. 2 f and Supplementary Table 4 ). TBAT and tetrabutylammonium bromide (TBAB) exhibit comparatively higher and more stable selectivity (73.3 ~ 93.7% and 75.1 ~ 85.3%, respectively) compared with other four electrolytes. To explain these phenomena, the conversion and yield distribution in different concentrations of electrolytes are analyzed ( Supplementary Fig. 17, 18 and note 12 ). On the whole, the increased electrolyte concentration promotes the competitive reactions (hydrodechlorination in in TBAT, TBAB, LiClO 4 , LiOAc and LiOAc·2H 2 O, and self-coupling reaction in TMAH) in electrocatalysis process to varying degrees, resulting in the decline of MCN selectivity in overall products. Second, it can also influence the selectivity in chemical reactions by investigating the MCN selectivity in Path 2 (Sel. MCN (Path2)) obtained by the electrochemical reaction starting from TCMP and the chemical reaction starting from theoretically equimolar CNC ( Supplementary Fig. 19 and note 13 ). To elucidate the correlation between electrolyte and selectivity of MCN in Path 2 , the solution pH under different variety and concentration of electrolytes was measured ( Supplementary Tables 5 and 6 ). As depicted in Supplementary Fig. 20 , the acidic environment is conducive to the formation of MCN with high selectivity and the selectivity of MCN decreases with pH increasing. Based on the above results, the optimal performance with conversion of 99.2%, yield of 92.5%, and selectivity of 93.2% for MCN production can be obtained at the potential of − 0.6 V in 0.03 M TBAT solution using CH 3 OH as solvent under continuous O 2 feeding. The durability was evaluated by performing 30 consecutive cyclic tests (180 h). As shown in Fig. 2 g, the yield and selectivity of MCN remain at ~ 90.8 and 93.4%, respectively, manifesting the excellent outstanding reusability and stability of this system. The four electrons transferred Faradaic efficiency (FE) with ~ 44.1% can be seen, and the number of electrons transferred to form MCN is calculated by *O formation. The remaining electrons can be used for the production of other ROSs in ORR, which is possible to produce MCN. FE calculated by ROSs using different numbers of electrons are recorded in Supplementary Note 14 . The Ag (a) electrode after electrocatalysis for 30 cycles was characterized by SEM and XPS ( Supplementary Figs. 21 and 22 ), revealing the high durability. Moreover, a technoeconomic analysis (TEA) on the plant-gate levelized costs was performed to evaluate the profitability of this technology 37 – 39 , and the details of TEA are available in Supplementary Fig. 23 and Note 15 . Figure 2 h shows the profitable regions for MCN generation as a function of FE and electricity cost. The calculations indicate a profit of 2328.3 US $ per ton can be seen for MCN generation using this system as shown in the marked star. Even with a relatively high electricity price (0.2 $ kW h − 1 ), this technology still shows the good economic benefits, suggesting the promising potential in practical production. Furthermore, by regulating the electrolyte, atmosphere and potential conditions, the other products, CMP and CNA with high selectivity of 99.4 and 96.1%, respectively, were achieved ( Supplementary Figs. 24 and 25 ). Mechanistic studies Electrochemical in-situ characterizations were conducted to monitor some key intermediates. As depicted in in-situ Raman spectra (Fig. 3 a), the characteristic peaks of oxygen intermediate at 1050 and 1150 cm − 1 attributed to the adsorbed intermediates species (*OH and *O 2 ) on the surface of catalyst 40 – 42 , respectively, imply the occurrence of ORR (O 2 + * → *O 2 , *O 2 + H + + e − → *OOH, *OOH + H + + e − → *O + H 2 O, *O + H + + e − → *OH, *OH + H + + e − → H 2 O) 43 – 45 . The increasing intensity of peaks in potential-dependent in-situ Raman spectra manifest ORR starts at the potential of − 0.2 V, in accordance with LSV and electrolytic results ( Supplementary Fig. 26 ). Two peaks located at 1450 and 1650 cm − 1 are corresponding to C-Cl bonds of TCMP. The C-Cl bond at 1450 cm − 1 appears later (about 0.3 V) than that at 1650 cm − 1 with the increasing potential, suggesting the stepwise dechloridation ( Supplementary Fig. 27 ) 46 . The simultaneous appearance of characteristic peaks ascribed to dechloridation and ORR in Fig. 3 b confirms the coupled reaction 37 , 47 . In the presence of O 2 , the earlier initiation of ORR than dechlorination leads to a switch from single hydrodechlorination to ORR-coupled dechlorination reaction. Time-dependent in-situ Raman spectra at the potential of − 0.6 V shows the inconspicuous growth of peak at 1450 and 1650 cm − 1 , illustrating the C-Cl bonds are broken continuously ( Supplementary Fig. 28 ). Meanwhile, the adsorbed OH and O 2 at 1050 and 1150 cm − 1 also suggest the steady coupling reaction. Furthermore, the generated products and intermediates were detected via in-situ FTIR spectroscopy ( Supplementary Fig. 29 ). Under the condition of O 2 -particapted CH 3 OH solution, the upward peaks at 1040, 1160, and 1443 cm − 1 are attributed to the stretching mode of *O 2 , OOH*, and *OH, respectively, suggesting the ORR process (Fig. 3 c and Supplementary Fig. 30 ) 48 , 49 . The absorption bands at 1588, and 3450 cm − 1 assigned to the bending vibration and stretching mode of O─H affirm the generation of water molecules from ORR 50 , 51 . When containing TCMP in solution, C = C skeletal vibration of the pyridine ring was observed at 1660 cm − 1 , corresponding to the adsorbed TCMP on the electrode surface. The peak at 1240 cm − 1 assigned to the stretching band of C-Cl with a tendency of first rising (from 0.2 to − 0.6 V) and then descend manifests the adsorption and consumption of TCMP. Notably, the weak peak at 1705 cm − 1 is the stretching vibration of C = O, implying the transient existence of CNC on the surface of electrode. On the other hand, under the condition of N 2 -pumped CH 3 OH solution with TCMP, two upward peaks corresponding to CH and CH 2 observed at 1105 and 1410 cm − 1 indicate the formation of new CH/CH 2 bonds by hydrodechlorination ( Supplementary Fig. 31 ) 52 , 53 . In-situ electron paramagnetic resonance (EPR) spectra were conducted by using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and 5-(deisopropoxyphosphoryl)-5-methyl-1-pyrroline-N-oxide (DIPPMPO) as the radical trapping reagents 54 – 56 . As demonstrated in Fig. 3 d, Supplementary Fig. 32 and Note 16 , ROSs (•OH, •OOH, and •O) can be captured by DMPO during the electrocatalytic process, implying the ORR process. No signal of •H can be seen when using DMPO as trapping reagents, suggesting that hydrogenation process is difficult to occur. The descend of peak intensity of ROSs after the addition of TCMP verifies the consumption of oxygen intermediates. A gradually increased twelve-fold signal with increasing of potential is corresponded to DIPPMPO- •C, suggesting the activation of TCMP ( Supplementary Fig. 33 ). To further distinguish the source of •C (TCMP or CH 3 OH), the comparison of EPR spectra was performed. As shown in Fig. 3 e and Supplementary Fig. 34 , no signal can be found in the absence of TCMP, whereas the signal becomes stronger with time in presence of TCMP in solution, affirming the captured •C comes from the activation of TCMP. The above results affirm the concurrence of ORR and dechloridation. Besides, the hydrodechlorination process of Path 1 is also verified by the distinct nine-fold (1:1:2:1:2:1:2:1:1) signal of *H verify the ( Supplementary Fig. 35 ) 57 . Theoretically, the electrochemical ORR-coupled dechlorination reaction may undergo two paths according to the sequence of dechlorination and oxygen bonding, which can be distinguished by different free radicals ( Supplementary Fig. 36 ). As displayed in femtosecond transient absorption spectra (fs-TAS, Fig. 3 f) 58 , 59 , the enhanced signal at 432 nm confirms the presence of carbene species, illustrating that the mechanism of CNC generation follows a first dechlorination via 2e reaction and then oxygen insertion route (C 6 H 3 Cl 4 N* → C 6 H 3 Cl 3 N* → C 6 H 3 Cl 2 N* → C 6 H 3 Cl 2 NO*). Additionally, the transient CNC was detected by LCMS analysis ( Supplementary Fig. 37 ). Isotope labeling experiments with the assistance of LCMS were carried out to track the oxygen source. As shown in Fig. 3 g, the peaks with mass-to-charge ratio ( m / z ) of 159.55 and 173.58 assigned to the signals of C 6 H 5 ClNO 18 O (CNA- 18 O) and C 7 H 7 ClNO 18 O (MCN- 18 O) fragments, respectively, confirm the participation of O 2 in the electrochemical process of CNC generation via forming C = 18 O bond. Notably, the peaks at m / z of 161.55 corresponded to C 6 H 5 ClN 18 O 2 indicated that the source of H 2 O participated in nucleophilic reaction for CNA generation comes from the ORR process. In addition, the chemical nucleophilic reaction for MCN generation was investigated through replacing CH 3 OH with deuterated CH 3 OH (CD 3 OD) solution ( Supplementary Fig. 38 ). The appearance of deuterated methyl group verifies CH 3 OH as the nucleophilic reagent participating in the chemical reaction for MCN generation. Density functional theory (DFT) calculations were conducted to further unravel the effect of intermediates on the reaction mechanism. The free energy diagram for oxygen intermediates along the 2e − dechlorination - oxygen insertion pathway on Ag (111) are depicted in Fig. 4 a and Supplementary Fig. 39 . The elevated energy barrier for C-Cl bond breaking (1.16 and 1.43 eV) indicates the 2e − dechlorination is endothermic and the forming of adsorbed carbene (C 6 H 3 Cl 2 N*) is rate-determining step (RDS) in the whole reaction for MCN synthesis, while the adsorption and oxygen insertion processes of oxygen intermediates (O*, OOH*, OH*) are exergonic in free energy, implying the coupling process between carbene and oxygen intermediates are spontaneous. The larger exergonic energy in oxygen insertion processes of O* than those of OOH*, OH* demonstrates O* is more favorable. Moreover, the energy level profile and corresponding adsorption configurations for hydrodechlorination of TCMP are shown in Supplementary Figs. 40 and 41 , and the less exothermic energy in hydrogenation process (C 6 H 3 Cl 3 N* + H*→ C 6 H 4 Cl 3 N*, et. al.) than in oxygenation reaction (C 6 H 3 Cl 2 N* + O*→C 6 H 3 Cl 2 NO*) in Fig. 4 b indicates the superior competition of ORR-coupled dechlorination reaction than hydrodechlorination reaction. In the chemical nucleophilic steps for MCN and CNA generation, desorption is the endothermic processes (Fig. 4 a and Supplementary Fig. 42 ). As depicted in Fig. 4 b, the endothermic dechlorination process is the RDS for electrocatalytic CNC synthesis. More importantly, the sequence of dechlorination and oxygenation was explored by contrasting free energy steps. The oxygenation-dechlorination process (C 6 H 3 Cl 3 N* → C 6 H 3 Cl 2 N* + O*) exhibits lower free energy of RDS (1.48 eV) than that of the oxygenation-dechlorination process (C 6 H 3 Cl 3 NO* → C 6 H 3 Cl 2 NO*, 1.81 eV), verifying the route follows first dechlorination and then oxygenation for CNC generation. Based on the above investigations, a mechanism of the electrocatalytic ORR–coupled dechlorination cascading chemical nucleophilic reaction were proposed, as described in Fig. 4 c. (Ⅰ) TCMP dechlorination activation: the adsorbed TCMP molecule undergoes twice breaking of C-Cl bonds, and carbene intermediate are formed through 2e − process. (Ⅱ) O 2 activation by ORR: the absorbed O 2 molecule is reduced by gradually obtaining electrons and protons (produced from anode chamber or CH 3 OH), and oxygen intermediates are generated by the 4e − process (O 2 → OOH* → O* → OH*). (Ⅲ) CNC is produced through the combination of carbene and oxygen intermediates. (Ⅳ) A chemical nucleophilic reaction happens between CNC and CH 3 OH to form MCN. Universality of esters production and application of flow electrolyzer The universality of electrocatalytic ORR-coupled dechlorination cascading chemical reaction of trichloromethyl compounds over Ag (a) electrode was evaluated (Fig. 5 a, Supplementary Fig. 43–50 , and Table 7 ). Various functionalized substrates containing benzene and pyridine rings reacting with different nucleophilic reagents can be transformed into corresponding esters with high yields (58.8 ~ 86.4%) and selectivity (69.2 ~ 100%). To assess the feasibility of this system for practically industrial applications, a two-electrode flow electrolyzer (4 cm 2 ) with Ag (a) cathode and carbon paper anode was used for MCN production (Fig. 5 b and Supplementary Fig. 51 ). The O 2 -saturated electrolyte containing 20 mM TCMP in 0.03 M TBAT methanol solution was circulated in the flow cell by using a gas-liquid mixed flow pump. The result of constant current electrocatalysis (− 5 mA cm − 2 ) in Fig. 5 c shows a 91.6% of yield and 94.9% of selectivity in 6 h, affirming the superiority and promising utilization of this strategy. Moreover, the results of long-term electrocatalysis for 60 h are displayed in Fig. 5 d. The sustained voltage (− 2.2 V), MCN yield rate (8.3 mg h − 1 cm − 2 ), and four electrons transferred FE (48.5%) demonstrate the excellent stability and reusability of Ag (a) electrode. Conclusion In conclusion, this work presents a highly efficient cascaded approach of electrochemical and chemical reactions for ester production using TCMP as the substrate. The reaction pathway is redirected from conventional hydrodechlorination to the dechlorination-oxygen insertion process by introducing O 2 . The high reactivity for CNC generation in electrochemical reaction and an acid environment in chemical nucleophilic reaction facilitate a 93.2% selectivity for MCN synthesis. Mechanistic insights suggest that the electrocatalytic process involves an ORR-coupled dechlorination reaction, in which ROSs play a crucial role in generating intermediate CNC. This cascade system of electrochemical and chemical reactions demonstrates excellent performance and scalability, offering a promising alternative to traditional ester production methods, with broad applicability for sustainable industrial processes. Methods Chemicals and Materials Deionized water and Wahaha water (liquid phase mobile phase only, Hangzhou Wahaha Group CO., Ltd) were used in all the experiments, and deionized water was prepared by the reverse osmosis deionized water machine (Hitech Instruments CO., Ltd) in laboratory. Ag net (100-mesh, 99.99%), Cu net (100-mesh, 99.99%), and Co plate (99.99%) were purchased from Qinghe Yuqian Metal Materials Co., Ltd. Phosphoric acid (H 3 PO 4 , ≥ 85%), nitric acid (HNO 3 , 65.0–68.0%), hydrofluoric acid (HF, ≥ 40.0%), hydrochloric acid (HCl, 36.0 ~ 38.0%), sulfuric acid (H 2 SO 4 , 95.0 ~ 98.0%), methanol anhydrous (CH 3 OH, ≥ 99.7%), ethanol absolute (C 2 H 5 OH, ≥ 99.7%), acetonitrile (CH 3 CN, ≥ 99.5%), hydrogen peroxide aqueous solution (H 2 O 2 , ≥ 30%), and ammonium fluoride (NH 4 F, ≥ 96.0%) were purchased from Sinopharm Chemical Reagent Co., Ltd (SCR). Methyl alcohol (CH 3 OH, 99.9%) and acetonitrile (CH 3 CN, 99.9%) were purchased from Tedia Company, Inc. Lithium acetate dihydrate (LiOAc·2H 2 O, 99%), lithium acetate (LiOAc, 99.99%), 6-chloronicotinic acid (C 6 H 4 ClNO 2 , CNA, 98%), 2-chloro-5-(trichloromethyl)pyridine (C 6 H 3 Cl 4 N, TCMP, 98%), and 2-chlorobenzotrichloride (C 7 H 4 Cl 4 , ≥ 95%) were purchased from Shanghai Macklin Biochemical Co., Ltd (MACKLIN). Methyl 6-chloronicotinate (C 7 H 6 ClNO 2 , MCN, 99%), α,α,α,α',α',α'-hexachloro-p-xylene (C 8 H 4 Cl 6 , 98%), dimethyl terephthalate (C 10 H 10 O 4 , 99%), 4-fluorobenzotrichloride (C 7 H 4 Cl 3 F, 98%), methyl 2-chloropyridine-3-carboxylate (C 7 H 6 ClNO 2 , 99.9%), and methanol d4 (CD 3 OD, 99.8%) were purchased from Meryer Chemical Technology Co., Ltd (MERYER). Methyl benzoate (C 8 H 8 O 2 , > 99.5%), methyl 2-chlorobenzoate (C 8 H 7 ClO 2 , > 98.0%), tetrabutylammonium tetrafluoroborate (C 16 H 36 BF 4 N, TBAT, ≥ 98.0%), tetramethylammonium hydroxide ((CH 3 ) 4 NOH, TMAH, 25%), 6-chloronicotinoyl chloride (C 6 H 3 Cl 2 NO, CNC, 98%), lithium perchlorate (LiClO 4 , 99.99%), and tetrabutylammonium bromide (C 16 H 36 BrN, TBAB, 99.0%) were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd (aladdin). Trichlorotoluene (C 7 H 5 Cl 3 , > 99.0%) were purchased from Tokyo Chemical Industry Co., Ltd. Ethyl 6-chloropyridine 3-carboxylate (C 8 H 8 ClNO 2 , > 97%), methyl 6-chloropyridine-2-carboxylate (C 7 H 6 ClNO 2 , ≥ 98%), and methyl 4-chlorobenzoate (C 14 H 11 ClO 2 , ≥ 98%) were purchased from Accela ChemBio Co., Ltd (Accela). 2-Chloro-6-(trichloromethyl)pyridine (C 6 H 3 Cl 4 N, 99.0%), and 2-chloro-5-methyloyridine (C 6 H 6 ClN, CMP 98.38%) were purchased from Bide Pharmatech Co., Ltd. 2-Chloro-3-(trichloromethyl)pyridine (C 6 H 3 F 4 N, 97%) was purchased from Shanghai Yuanye Bio-Technology Co., Ltd. 4-Chlorobenzotrichloride (C 7 H 4 Cl 4 , 98%) was purchased from Shanghai Adamas Reagent Co., Ltd (Damas-beta). Methyl 4-fluorobenzoate (C 8 H 7 FO 2 , 99%) was purchased from J&K Scientific Co., Ltd. 2-Chloro-5-chloromethylpyridine (C 6 H 6 ClN, CCMP, 98%) was purchased from Shanghai URChem Ltd. Ethyl 6-chloropyridine-2-carboxylate (C 8 H 8 ClNO 2 , 97%) and ethyl 2-chloropyridine-3-carboxylate (C 8 H 8 ClNO 2 , 98%) was purchased from Shanghai Yi En Chemical Technology Co., Ltd. Isotopic Oxygen- 18 O 2 (≥ 99%) was purchased from Wuhan Isotope Technology Co., Ltd. Except noted, all chemicals were used without further purification. Preparation of catalysts Ag (a) electrode The activated Ag electrode (Ag (a) ) was prepared through the electrochemical cyclic voltammetry (CV) activation treatments. Initially, a 1 × 2 cm 2 piece of Ag mesh was ultrasonicated sequentially in ethanol and deionized water for 10 min to remove surface impurities. Then, the CV process was conducted in an undivided cell containing 1 M HCl solution. The platinum plate, washed Ag mesh and saturated calomel electrode (SCE) were used as the counter electrode, working electrode, and reference electrode, respectively. Specifically, the washed mesh net was activated in the range of − 1.0 to 1.3 V vs SCE at a scan rate of 50 mV s − 1 for 10 cycles. The obtained Ag (a) electrode was rinsed with deionized water and then dried. For comparison, the activated Cu mesh (Cu (a) ) and Co plate (Co (a) ) electrodes were synthesized by the same procedure. Characterizations Scanning electron microscopy (SEM) images were obtained from a German ZEISS Gemini SEM with an accelerating voltage of 20 kV. Transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM, Tecnai G2 F30) images were acquired at an operating voltage of 300 kV. X-ray diffraction (XRD) patterns were performed by the X’Pert PRO XRD diffractometer from PANalytical, Netherlands, with a Cu Kα radiation (λ = 0.1541 nm). X-ray photoelectron spectroscopy (XPS) measured were carried out on a Thermo Scientific K-Alpha X-ray photoelectron spectrometer using the Al Kα source at a chamber pressure of 2 × 10 − ⁷ mbar. The PHS-3C pH meter (Thunder Magnetic, Shanghai Yidian Scientific Instrument Co., Ltd.) was used to measure the solution pH. Electrochemical measurements The electrochemical experiments were performed in a three-electrode H-cell (separated by Nafion 117 membrane) on the CHI 760E workstation (CH Instruments Inc., Shanghai) without any iR -compensation, where Pt plate (1 × 2 cm 2 ), Ag (a) electrode (1 × 2 cm 2 ), and Ag/AgCl (saturated KCl) electrode were used as a counter, working, and reference electrodes, respectively. Notably, all potentials for electrocatalysis in the three-electrode H-cell are reported with respect to the Ag/AgCl electrode in this paper. The cathode compartment was filled with 40 mL of different concentrations (0.01, 0.03, 0.3, and 0.5 M) of electrolytes (TBAT, TBAB, TMAH, LiOAc, LiOAc·2H 2 O, and LiClO 4 ) in CH 3 OH solvent, with or without 10 mM TCMP. The anode compartment was filled with 1 M H 2 SO 4 . Before all the electrochemical measurements, the inert nitrogen (N 2 ) was introduced into solution for 20 min to remove the undesired side reactions. Then different gases (N 2 , air, or O 2 ) with the flow rate of 0.2 L min − 1 were purged into the electrolyte during the whole test. Linear sweep voltammetry (LSV) tests were conducted in the three-electrodes system at a scan rate of 10 mV s − 1 . In-situ electrochemical impedance spectroscopy (EIS) was employed on a ZAHNER Zennium electrochemical workstation over the frequency of 0.01 ~ 10 5 Hz at potential range from 0.2 to − 1.4 V vs Ag/AgCl (an interval of 0.2 V) with or without TCMP and O 2 . Chronopotentiometry was used for electrolysis under different conditions. The two-electrode flow electrolyzer consists of anode and cathode chambers, assembled with stainless steel bolts and sealed with washers. Carbon paper and Ag (a) electrodes (2 × 2 cm − 2 ) were used as a counter and working electrodes, respectively, using the Nafion 117 proton membrane for separation. During the test, high purity O 2 was fed into the cathode storage tank at a rate of 0.2 L·min − 1 . The anolyte was 30 mL 1 M H 2 SO 4 , and the catholyte was 30 mL 20 mM TCMP with 30 mM TBAT in CH 3 OH. Two peristaltic pumps were used to transport the solution to the chambers. In-situ Raman spectra Electrochemical in-situ Raman spectra were detected on the high-speed and high-resolution confocal Raman spectrometer (LabRAM Odyssey, HORIBA France SAS) with the excitation wavelength of 532 nm. 0.3 M LiOAc·2H 2 O solution using CH 3 OH as solvent with or without TCMP (10 mM) in O 2 or N 2 saturated environment was used as the electrolyte. The applied potential was carried out from OCP to − 1.4 V vs Ag/AgCl with an interval of 0.1 V. In-situ FTIR spectra Electrochemical in-situ Fourier transform infrared spectra (FTIR) was measured by Bruker INVENIO-S (Bruker Optics GmbH&Co. KG) using attenuated total reflection (ATR) mode. Concretely, 2 mg catalyst was dispersed into the mixture of ethanol (400 µL) and Nafion (100 µL) for sonication (30 min). The as-prepared catalyst ink (2 mg) was applied to the surface of the gold-plated silicon crystal, assembling as a working electrode. The measurements were conducted in a spectra-electrochemical cell containing 30 mM TBAT methanol solution with or without TCMP and O 2 . The spectra were collected at various potentials from OCP to − 1.4 V vs Ag/AgCl with an interval of 0.1 V. EPR experiment Electron paramagnetic resonance (EPR) spectra were recorded on a Bruker A300 spectrophotometer (Germany) using 20 mW microwave power and 100 kHz field modulation with the amplitude of 1 G. The g-values for each EPR spectrum were extracted from simulations performed using EasySpin (v5.2.23). The sample was prepared by the following process: 10 mg catalyst was dispersed in CH 3 OH (5 mL) under sonication. Before testing, 200 µL of the mixed solution was taken out, followed by the addition of 100 µL of capture agents. The time-dependent spectra were collected at the potentials of − 0.6 V vs Ag/AgCl. Products analysis The concentration of TCMP and its products in the reaction system were quantified using a Thermo Scientific Dionex Ultimate 3000 high-performance liquid chromatography (HPLC) system. The HPLC system was equipped with a chromatographic column (Ultimate AQ-C18, 250 mm × 4.6 mm, 5 µm) and a UV-visible detector (λ = 230 nm) to ensure effective separation of reactants and products. A sample volume of 10 µL was injected, and the column temperature was maintained at 35℃. The mobile phase for the HPLC consisted of 0.03 M H 3 PO₄, CH 3 OH, and acetonitrile, with a flow rate of 1 mL·min⁻¹ using a gradient elution method. The performance evaluation indicators include conversion (Con.), selectivity (Sel.), yield and Faradaic efficiency (FE) based on the following equation: $$\\:\\text{C}\\text{o}\\text{n}.\\left(\\text{%}\\right)=\\frac{\\text{C}\\text{o}\\text{n}\\text{s}\\text{u}\\text{m}\\text{p}\\text{t}\\text{i}\\text{o}\\text{n}\\:\\text{o}\\text{f}\\:\\text{r}\\text{e}\\text{a}\\text{c}\\text{t}\\text{a}\\text{n}\\text{t}\\text{s}}{\\text{T}\\text{h}\\text{e}\\:\\text{t}\\text{o}\\text{t}\\text{a}\\text{l}\\:\\text{a}\\text{m}\\text{o}\\text{u}\\text{n}\\text{t}\\:\\text{o}\\text{f}\\:\\text{r}\\text{e}\\text{a}\\text{c}\\text{t}\\text{a}\\text{n}\\text{t}\\text{s}}\\times\\:100\\:\\text{%}$$ 1 $$\\:\\text{S}\\text{e}\\text{l}.\\:\\left(\\text{%}\\right)=\\frac{\\text{T}\\text{h}\\text{e}\\:\\text{a}\\text{m}\\text{o}\\text{u}\\text{n}\\text{t}\\:\\text{o}\\text{f}\\:\\text{t}\\text{a}\\text{r}\\text{g}\\text{e}\\text{t}\\:\\text{p}\\text{r}\\text{o}\\text{d}\\text{u}\\text{c}\\text{t}\\:}{\\text{C}\\text{o}\\text{n}\\text{s}\\text{u}\\text{m}\\text{p}\\text{t}\\text{i}\\text{o}\\text{n}\\:\\text{o}\\text{f}\\:\\text{r}\\text{e}\\text{a}\\text{c}\\text{t}\\text{a}\\text{n}\\text{t}\\text{s}}\\times\\:100\\:\\text{%}$$ 2 $$\\:\\text{Y}\\text{i}\\text{e}\\text{l}\\text{d}\\:\\left(\\text{%}\\right)=\\frac{\\text{T}\\text{h}\\text{e}\\:\\text{a}\\text{m}\\text{o}\\text{u}\\text{n}\\text{t}\\:\\text{o}\\text{f}\\:\\text{t}\\text{a}\\text{r}\\text{g}\\text{e}\\text{t}\\:\\text{p}\\text{r}\\text{o}\\text{d}\\text{u}\\text{c}\\text{t}\\:}{\\text{T}\\text{h}\\text{e}\\:\\text{t}\\text{o}\\text{t}\\text{a}\\text{l}\\:\\text{a}\\text{m}\\text{o}\\text{u}\\text{n}\\text{t}\\:\\text{o}\\text{f}\\:\\text{r}\\text{e}\\text{a}\\text{c}\\text{t}\\text{a}\\text{n}\\text{t}\\text{s}}\\times\\:100\\:\\text{%}$$ 3 $$\\:\\text{F}\\text{E}\\:\\left(\\text{%}\\right)=\\frac{n\\times\\:\\text{T}\\text{h}\\text{e}\\:\\text{a}\\text{m}\\text{o}\\text{u}\\text{n}\\text{t}\\:\\text{o}\\text{f}\\:\\text{t}\\text{a}\\text{r}\\text{g}\\text{e}\\text{t}\\:\\text{p}\\text{r}\\text{o}\\text{d}\\text{u}\\text{c}\\text{t}\\:\\left(\\text{m}\\text{o}\\text{l}\\right)\\times\\:F}{\\text{T}\\text{h}\\text{e}\\text{o}\\text{r}\\text{e}\\text{t}\\text{i}\\text{c}\\text{a}\\text{l}\\:\\text{c}\\text{o}\\text{n}\\text{s}\\text{u}\\text{m}\\text{p}\\text{t}\\text{i}\\text{o}\\text{n}\\:\\text{o}\\text{f}\\:\\text{t}\\text{o}\\text{t}\\text{a}\\text{l}\\:\\text{c}\\text{h}\\text{a}\\text{r}\\text{g}\\text{e}}\\times\\:100\\:\\text{%}$$ 4 where n represents the number of electrons transferred to form MCN, and F is the Faraday constant (96,485 C·mol − 1 ). fs-TAS Femtosecond transient absorption spectroscopy (fs-TAS) was performed on Ultrafast Systems Helios (USA), and the parameters used in the experiment are as follows: Pump energy: 962 µW; Pump wavelength: 350 nm; Cuvette length: 2 mm; Comments: time zero: 114.453 ps; Averaging time: 0.3 s; Number of scans: 2; Measurement time: 00:11:26; Time units: ps. The absorption spectra of transient products can be obtained by detecting the absorption of light, allowing for direct detection of transient products based on the absorption spectra. Isotope labeling experiments 18 O 2 (≥ 99%, Wuhan Isotope Technology Co., Ltd) was used as the oxygen source to label substrate. The isotope labeling experiments were carried out in an H-type electrolytic cell containing 1 M H 2 SO 4 anolyte and 30 mM LiOAc·2H 2 O (TBAT as solvent) catholyte with 10 mM TCMP. The electrolysis was taken out for 6 h at the potential of -0.6 V vs Ag/AgCl. Then, the sample was analyzed by LCMS. The H isotope tracing was also conducted using CD 3 OD (99.8%, MERYER) instead of CH 3 OH solvent. LCMS determination LCMS was performed on Agilent 1290uplc-QTOF6550 instrument. The specific parameters are as follows: Mobile phase A: 0.1% formic acid aqueous solution; Mobile phase B: methanol acetonitrile = 1:1 solution; The ratio of phase A to phase B is 70 : 30, The flow rate: 0.3 mL min − 1 ; The injection volume: 5 µL; Chromatographic column: Waters BEH C18 ( inner diameter: 2.1 mm; column length: 100 mm; and particle size: 1.7 µm); Mass spectrometry scanning range: primary 50–600 m/z; Sheath gas temp 350 ℃; Sheath gas flow 12 L min − 1 ; ESI mode: voltage 3200 V. DFT calculations All calculations were performed with periodic DFT using the Gaussian plane wave method implemented in CP2K’s Quickstep module 60 , 61 . The explorative studies of the catalysts structure were performed using the molecularly optimized basis set DZVP-MOLOPT-SR-GTH for each atom with a Goedecker-Teter-Hutter (GTH) pseudopotential 62 . The calculations were conducted using the generalized gradient approximation and the Perdew-Burke-Ernzerhof (PBE) functional 63 with DFT-D3 correction 64 , 65 . An energy convergence for the self-consistent field (SCF) calculation was set to 2 × 10 − 6 Hartree. An energy cutoff of 400 Ry was used throughout the calculations. The input file was generated by Multiwfn 66 . A 3 × 3 × 1 supercell with 3-layer atoms was employed for Ag (111) surfaces model according to the maximum crystal facet in XRD. The vacuum slab was 10 Å to minimize the interaction between slabs. In order to obtain more precise energy, the TZV2P-MOLOPT-PBE-GTH basis set with 3 × 3 × 1 k -points was employed and the cutoff energy further increase to 400 eV when calculated single point energy. The Gibbs free energy for each reaction intermediate is defined as fellow equation: \\(\\:G={E}_{DFT}+{E}_{ZPE}-TS\\) E DFT is the total energy of reaction intermediate model. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {\"props\":{\"pageProps\":{\"initialData\":{\"identity\":\"rs-5948207\",\"acceptedTermsAndConditions\":true,\"allowDirectSubmit\":true,\"archivedVersions\":[],\"articleType\":\"Article\",\"associatedPublications\":[],\"authors\":[{\"id\":434372598,\"identity\":\"109cdde7-ac39-4f81-af0c-9b3f70055730\",\"order_by\":0,\"name\":\"Huajun Zheng\",\"email\":\"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA40lEQVRIie3PMQrCMBSA4RcKcQm6poj2CkpBBy/TItilKm4ODk+ErK4FBa/g6FgQMsU76OKsg6KLmPYAMW6C+SGEwPsID8Dl+sW4PgRpEyAvnp49CTUh+A2BGMvLhgSrhTzddtVkM1fdI0x7MVYOuZGQtUzChqLDOao2gkpiZKPISDyeduq+oMMFaELEPkbOWkZC+fhekISW5GVBGE+pfxU0YiVBC8L5oFMngrYzkJMs0osJlppJkPXP/lPIIMj228tl1mssK8pMijwGUv+XA0TFdh/ndeQBM4Aa2sy6XC7XP/YGMstDpPGCWzgAAAAASUVORK5CYII=\",\"orcid\":\"https://orcid.org/0000-0002-4524-6456\",\"institution\":\"Zhejiang University of Technology\",\"correspondingAuthor\":true,\"prefix\":\"\",\"firstName\":\"Huajun\",\"middleName\":\"\",\"lastName\":\"Zheng\",\"suffix\":\"\"},{\"id\":434372599,\"identity\":\"d17f6fa0-cb68-4867-a255-b5cce255731a\",\"order_by\":1,\"name\":\"Zhefei Zhao\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"Zhejiang University of Technology\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Zhefei\",\"middleName\":\"\",\"lastName\":\"Zhao\",\"suffix\":\"\"},{\"id\":434372600,\"identity\":\"07238ed2-42e1-4053-b00c-7d9db5c11c9a\",\"order_by\":2,\"name\":\"Linlin Zhang\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"Zhejiang University of Technology\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Linlin\",\"middleName\":\"\",\"lastName\":\"Zhang\",\"suffix\":\"\"},{\"id\":434372601,\"identity\":\"d9f0dbc2-e8f8-4b1a-8459-02f0165a5ea3\",\"order_by\":3,\"name\":\"Minhao Chen\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"Zhejiang University of Technology\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Minhao\",\"middleName\":\"\",\"lastName\":\"Chen\",\"suffix\":\"\"},{\"id\":434372602,\"identity\":\"bdc71756-820f-4673-979f-1a5562ce11bc\",\"order_by\":4,\"name\":\"Ruopeng Yu\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"Zhejiang University of Technology\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Ruopeng\",\"middleName\":\"\",\"lastName\":\"Yu\",\"suffix\":\"\"},{\"id\":434372603,\"identity\":\"574c73d4-7a71-4d24-9fbc-4e31a8fa3f54\",\"order_by\":5,\"name\":\"Runtao Jin\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"Zhejiang University of Technology\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Runtao\",\"middleName\":\"\",\"lastName\":\"Jin\",\"suffix\":\"\"},{\"id\":434372604,\"identity\":\"e7594d97-1723-4a9d-a63f-1ce4cb9b8308\",\"order_by\":6,\"name\":\"Fengjiao Jian\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"Zhejiang University of Technology\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Fengjiao\",\"middleName\":\"\",\"lastName\":\"Jian\",\"suffix\":\"\"},{\"id\":434372605,\"identity\":\"dfdfd2af-1b69-4ec2-8341-3a06483c3047\",\"order_by\":7,\"name\":\"Shengyin Shui\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"Zhejiang University of Technology\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Shengyin\",\"middleName\":\"\",\"lastName\":\"Shui\",\"suffix\":\"\"},{\"id\":434372606,\"identity\":\"8e521081-9958-48a4-8287-d492751123d8\",\"order_by\":8,\"name\":\"Wenjie Yan\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"Zhejiang University of Technology\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Wenjie\",\"middleName\":\"\",\"lastName\":\"Yan\",\"suffix\":\"\"},{\"id\":434372607,\"identity\":\"c3d6594b-fcfb-4bda-827f-ed75b89947fb\",\"order_by\":9,\"name\":\"Zhiliang Wang\",\"email\":\"\",\"orcid\":\"https://orcid.org/0000-0003-2139-8495\",\"institution\":\"University of Queensland\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Zhiliang\",\"middleName\":\"\",\"lastName\":\"Wang\",\"suffix\":\"\"},{\"id\":434372608,\"identity\":\"4784fd0d-b833-430d-b077-f29c0765d50d\",\"order_by\":10,\"name\":\"Yinghua Xu\",\"email\":\"\",\"orcid\":\"https://orcid.org/0000-0001-9854-7845\",\"institution\":\"Zhejiang University of Technology\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Yinghua\",\"middleName\":\"\",\"lastName\":\"Xu\",\"suffix\":\"\"},{\"id\":434372609,\"identity\":\"a6779a35-5f42-4657-864b-c262ea5b7931\",\"order_by\":11,\"name\":\"Xinbiao Mao\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"Zhejiang University of Technology\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Xinbiao\",\"middleName\":\"\",\"lastName\":\"Mao\",\"suffix\":\"\"},{\"id\":434372610,\"identity\":\"e27bc26f-eeaa-4e71-b3a1-21d06fb61996\",\"order_by\":12,\"name\":\"Youqun Chu\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"Zhejiang University of Technology\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Youqun\",\"middleName\":\"\",\"lastName\":\"Chu\",\"suffix\":\"\"},{\"id\":434372611,\"identity\":\"283d1d1d-7208-4b03-a005-5a49e7b4f5e6\",\"order_by\":13,\"name\":\"Lianzhou Wang\",\"email\":\"\",\"orcid\":\"https://orcid.org/0000-0002-5947-306X\",\"institution\":\"Nanomaterials Center, School of Chemical Engineering and AIBN, the University of Queensland\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Lianzhou\",\"middleName\":\"\",\"lastName\":\"Wang\",\"suffix\":\"\"}],\"badges\":[],\"createdAt\":\"2025-02-03 04:10:24\",\"currentVersionCode\":1,\"declarations\":\"\",\"doi\":\"10.21203/rs.3.rs-5948207/v1\",\"doiUrl\":\"https://doi.org/10.21203/rs.3.rs-5948207/v1\",\"draftVersion\":[],\"editorialEvents\":[{\"content\":\"https://doi.org/10.1021/jacs.5c07666\",\"type\":\"published\",\"date\":\"2025-08-01T00:00:00+00:00\"}],\"editorialNote\":\"\",\"failedWorkflow\":false,\"files\":[{\"id\":79350244,\"identity\":\"d3d492e8-19ca-41a3-8ad3-8806bf442d7e\",\"added_by\":\"auto\",\"created_at\":\"2025-03-27 10:12:17\",\"extension\":\"png\",\"order_by\":1,\"title\":\"Figure 1\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":665723,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003e\\u003cstrong\\u003eSchematic illustration for comparisons of esters production pathways. a \\u003c/strong\\u003eThe conventional thermocatalytic route \\u003cem\\u003evia\\u003c/em\\u003e one-step process for esters synthesis. \\u003cstrong\\u003eb\\u003c/strong\\u003e The thermocatalytic route \\u003cem\\u003evia\\u003c/em\\u003etwo-step process for esters production. The process involves the production of intermediate, i.e., acyl chloride. \\u003cstrong\\u003ec\\u003c/strong\\u003e Photocatalytic strategy for esters production using trichloromethyl compounds as reactants. \\u003cstrong\\u003ed\\u003c/strong\\u003e Electrocatalytic strategy for esters synthesis in this work.\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"floatimage1.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-5948207/v1/19cb270b0b434a9894283094.png\"},{\"id\":79350247,\"identity\":\"3ecfd7f9-dcfd-48a8-91ce-26be904b4a18\",\"added_by\":\"auto\",\"created_at\":\"2025-03-27 10:12:17\",\"extension\":\"png\",\"order_by\":2,\"title\":\"Figure 2\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":1778954,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003e\\u003cstrong\\u003eDesign and performance toward MCN synthesis. a\\u003c/strong\\u003e Schematic diagram of TCMP reaction for O\\u003csub\\u003e2\\u003c/sub\\u003e-participated dechlorination reaction in H-type electrolytic cell. \\u003cstrong\\u003eb\\u003c/strong\\u003e LSV curves on Ag\\u003csub\\u003e(a)\\u003c/sub\\u003e electrode in 0.03 M TBAT solution (CH\\u003csub\\u003e3\\u003c/sub\\u003eOH or CH\\u003csub\\u003e3\\u003c/sub\\u003eCN as the solvent) with or without 10 mM TCMP and O\\u003csub\\u003e2\\u003c/sub\\u003e addition.\\u003cstrong\\u003e c\\u003c/strong\\u003e Yield distribution and conversion of TCMP at the potential of −0.6 V for 6 h electrolysis under various conditions including the changed solvents (CH\\u003csub\\u003e3\\u003c/sub\\u003eOH, CH\\u003csub\\u003e3\\u003c/sub\\u003eCN), and atmospheres (N\\u003csub\\u003e2\\u003c/sub\\u003e, O\\u003csub\\u003e2\\u003c/sub\\u003e) using 0.03 M TBAT as electrolyte.\\u003cstrong\\u003e d\\u003c/strong\\u003e Yield distribution and conversion of TCMP in the potential range of 0 to −1.4 V for 6 h electrolysis in 0.03 M TBAT solution (CH\\u003csub\\u003e3\\u003c/sub\\u003eOH as the solvent) in the presence (with shadow) or absence (without shadow) of O\\u003csub\\u003e2\\u003c/sub\\u003e.\\u003cstrong\\u003e e\\u003c/strong\\u003e Potential-dependent Bode phase plots over Ag(a) with TCMP in O\\u003csub\\u003e2\\u003c/sub\\u003e-saturated condition.\\u003cstrong\\u003e f\\u003c/strong\\u003e The selectivity of MCN at various kinds and concentrations of electrolytes.\\u003cstrong\\u003e g\\u003c/strong\\u003e Durability test at the potential of −0.6 V for 6 h electrolysis in 0.03 M TBAT solution (CH\\u003csub\\u003e3\\u003c/sub\\u003eOH as the solvent) in the presence of O\\u003csub\\u003e2\\u003c/sub\\u003e. \\u003cstrong\\u003eh\\u003c/strong\\u003e Technoeconomic analysis of the plant-gate levelized costs of MCN production.\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"floatimage2.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-5948207/v1/d2d6468c5c8b7d09d4dbaf4a.png\"},{\"id\":79350246,\"identity\":\"72479c64-1802-42bb-9709-e4da3f1a4e15\",\"added_by\":\"auto\",\"created_at\":\"2025-03-27 10:12:17\",\"extension\":\"png\",\"order_by\":3,\"title\":\"Figure 3\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":1316926,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003e\\u003cstrong\\u003eReaction mechanism exploration.\\u003c/strong\\u003e \\u003cstrong\\u003ea\\u003c/strong\\u003e \\u003cem\\u003eIn-situ\\u003c/em\\u003e Raman spectra collected at the potential of −0.6 V with TCMP in N\\u003csub\\u003e2\\u003c/sub\\u003e and without TCMP in O\\u003csub\\u003e2\\u003c/sub\\u003e. \\u003cstrong\\u003eb\\u003c/strong\\u003e Potential-dependent \\u003cem\\u003ein-situ\\u003c/em\\u003e Raman spectra with TCMP in O\\u003csub\\u003e2\\u003c/sub\\u003e. \\u003cstrong\\u003ec\\u003c/strong\\u003e Potential-dependent \\u003cem\\u003ein-situ \\u003c/em\\u003eFTIR spectra with TCMP in O\\u003csub\\u003e2\\u003c/sub\\u003e and the comparison of spectra between solution with and without TCMP. \\u003cstrong\\u003ed\\u003c/strong\\u003e Comparison of EPR spectra for trapping oxygen radicals before (blue line) and after (red line) adding TCMP in solution. \\u003cstrong\\u003ee\\u003c/strong\\u003e EPR spectra for trapping carbon radicals with and without TCMP in solution. \\u003cstrong\\u003ef \\u003c/strong\\u003efs-TAS spectra. \\u003cstrong\\u003eg\\u003c/strong\\u003e Isotope labeling results using \\u003csup\\u003e18\\u003c/sup\\u003eO\\u003csub\\u003e2\\u003c/sub\\u003e instead of O\\u003csub\\u003e2\\u003c/sub\\u003e.\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"floatimage3.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-5948207/v1/bb8ef26cd56007ae016049d7.png\"},{\"id\":79350245,\"identity\":\"a33e8be0-d69e-464c-8d92-9ea824428799\",\"added_by\":\"auto\",\"created_at\":\"2025-03-27 10:12:17\",\"extension\":\"png\",\"order_by\":4,\"title\":\"Figure 4\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":1852977,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003e\\u003cstrong\\u003eDFT calculation and proposed mechanism. a\\u003c/strong\\u003e Free energy diagram for MCN synthesis using different oxygen intermediates over Ag(111). \\u003cstrong\\u003eb\\u003c/strong\\u003e Free energy diagram for the ORR-coupled dechlorination cascading chemical reaction over Ag(111). \\u003cstrong\\u003ec\\u003c/strong\\u003e The proposed mechanism of MCN generation.\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"floatimage4.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-5948207/v1/c15bb973202346c9f0e2df57.png\"},{\"id\":79350249,\"identity\":\"ae12c76d-0d94-4d7a-89ea-e350a35cbeb3\",\"added_by\":\"auto\",\"created_at\":\"2025-03-27 10:12:17\",\"extension\":\"png\",\"order_by\":5,\"title\":\"Figure 5\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":861924,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003e\\u003cstrong\\u003eSubstrate scope and electrocatalysis in a two-electrode flow electrolyzer for MCN production. a\\u003c/strong\\u003e Substrate scope for the ORR-coupled dechlorination cascading chemical reaction over Ag\\u003csub\\u003e(a)\\u003c/sub\\u003e electrode. \\u003cstrong\\u003eb\\u003c/strong\\u003e Schematic illustration of the flow electrolyzer. \\u003cstrong\\u003ec\\u003c/strong\\u003e The yield and selectivity of MCN in the flow electrolyzer at −5 mA cm\\u003csup\\u003e−2\\u003c/sup\\u003e electrocatalysis. \\u003cstrong\\u003ed \\u003c/strong\\u003eA long-term electrolysis for 60 h (10 cycles) at constant current of −5 mA cm\\u003csup\\u003e−2\\u003c/sup\\u003e\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"floatimage5.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-5948207/v1/662fb8b8efbb94732770db7e.png\"},{\"id\":88663011,\"identity\":\"b1c5504e-1414-4539-8ed9-df41f322a2c8\",\"added_by\":\"auto\",\"created_at\":\"2025-08-08 21:47:17\",\"extension\":\"pdf\",\"order_by\":0,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"manuscript-pdf\",\"size\":7225339,\"visible\":true,\"origin\":\"\",\"legend\":\"\",\"description\":\"\",\"filename\":\"manuscript.pdf\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-5948207/v1/0c6271d9-c3ae-4716-8733-1f43c0174e57.pdf\"},{\"id\":79350257,\"identity\":\"b19ea1b1-8b1c-46f9-9866-ea77f34ef2f8\",\"added_by\":\"auto\",\"created_at\":\"2025-03-27 10:12:18\",\"extension\":\"docx\",\"order_by\":2,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"supplement\",\"size\":26812517,\"visible\":true,\"origin\":\"\",\"legend\":\"\",\"description\":\"\",\"filename\":\"SupportingInformation.docx\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-5948207/v1/049926efbfc27b74545a3e3e.docx\"}],\"financialInterests\":\"There is \\u003cb\\u003eNO\\u003c/b\\u003e Competing Interest.\",\"formattedTitle\":\"O\\u003csub\\u003e2\\u003c/sub\\u003e-Triggered Electrochemical Generation of Acyl Chloride Promoting Cascade Reaction of Esters Synthesis\",\"fulltext\":[{\"header\":\"Introduction\",\"content\":\"\\u003cp\\u003eEsters compounds as one of the most versatile and widely produced organic chemicals in industry, are widely used for lubricants\\u003csup\\u003e \\u003cspan citationid=\\\"CR1\\\" class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e \\u003c/sup\\u003e, emulsifiers\\u003csup\\u003e \\u003cspan citationid=\\\"CR2\\\" class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e \\u003c/sup\\u003e, dispersants\\u003csup\\u003e \\u003cspan citationid=\\\"CR3\\\" class=\\\"CitationRef\\\"\\u003e3\\u003c/span\\u003e \\u003c/sup\\u003e, industrial solvents\\u003csup\\u003e \\u003cspan citationid=\\\"CR4\\\" class=\\\"CitationRef\\\"\\u003e4\\u003c/span\\u003e \\u003c/sup\\u003e, cosmetic additives\\u003csup\\u003e \\u003cspan citationid=\\\"CR5\\\" class=\\\"CitationRef\\\"\\u003e5\\u003c/span\\u003e \\u003c/sup\\u003e, pharmaceutical intermediates\\u003csup\\u003e \\u003cspan citationid=\\\"CR6\\\" class=\\\"CitationRef\\\"\\u003e6\\u003c/span\\u003e \\u003c/sup\\u003e, food flavors\\u003csup\\u003e \\u003cspan citationid=\\\"CR7\\\" class=\\\"CitationRef\\\"\\u003e7\\u003c/span\\u003e \\u003c/sup\\u003e, pesticides\\u003csup\\u003e \\u003cspan citationid=\\\"CR8\\\" class=\\\"CitationRef\\\"\\u003e8\\u003c/span\\u003e \\u003c/sup\\u003e, plastics\\u003csup\\u003e \\u003cspan citationid=\\\"CR9\\\" class=\\\"CitationRef\\\"\\u003e9\\u003c/span\\u003e \\u003c/sup\\u003e, etc. Motivated by the accelerating market demand, the global market for esters is projected to reach US\\u003cspan\\u003e$\\u003c/span\\u003e27.8\\u0026nbsp;billion by 2029, growing at a compound annual rate (CAGR) of 6.4% from 2022 to 2029\\u003csup\\u003e10\\u003c/sup\\u003e. Currently, industrial production of esters predominantly relies on thermocatalytic strategy\\u003csup\\u003e \\u003cspan citationid=\\\"CR11\\\" class=\\\"CitationRef\\\"\\u003e11\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR12\\\" class=\\\"CitationRef\\\"\\u003e12\\u003c/span\\u003e \\u003c/sup\\u003e. The traditional esterification reaction is a well-established pathway due to its simplicity and wide applicability (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig1\\\" class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003ea)\\u003csup\\u003e \\u003cspan citationid=\\\"CR13\\\" class=\\\"CitationRef\\\"\\u003e13\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR14\\\" class=\\\"CitationRef\\\"\\u003e14\\u003c/span\\u003e \\u003c/sup\\u003e. However, this approach typically requires excessive reactants and operates under harsh conditions, such as the use of concentrated sulfuric acid, under elevated temperatures, and high pressures, leading to organic carbonization, poor product selectivity, and severe equipment corrosion, as well as intensive energy input and environmental concerns\\u003csup\\u003e \\u003cspan citationid=\\\"CR15\\\" class=\\\"CitationRef\\\"\\u003e15\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR16\\\" class=\\\"CitationRef\\\"\\u003e16\\u003c/span\\u003e \\u003c/sup\\u003e. To address these limitations, the acyl chloride esterification method was developed, involving transformation of organic acids to intermediate acyl chlorides and the subsequent nucleophilic reaction (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig1\\\" class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003eb)\\u003csup\\u003e \\u003cspan citationid=\\\"CR17\\\" class=\\\"CitationRef\\\"\\u003e17\\u003c/span\\u003e \\u003c/sup\\u003e. Generation of acyl chloride significantly enhance the reactivity of the subsequent nucleophilic reaction, enabling higher productivity and simpler ester separation\\u003csup\\u003e \\u003cspan citationid=\\\"CR18\\\" class=\\\"CitationRef\\\"\\u003e18\\u003c/span\\u003e \\u003c/sup\\u003e. Despite these advantages, the use of acylating agents such as thionyl chloride (SOCl₂)\\u003csup\\u003e \\u003cspan citationid=\\\"CR19\\\" class=\\\"CitationRef\\\"\\u003e19\\u003c/span\\u003e \\u003c/sup\\u003e, oxalyl chloride (C₂O₂Cl₂)\\u003csup\\u003e \\u003cspan citationid=\\\"CR20\\\" class=\\\"CitationRef\\\"\\u003e20\\u003c/span\\u003e \\u003c/sup\\u003e, phosgene (COCl₂)\\u003csup\\u003e \\u003cspan citationid=\\\"CR21\\\" class=\\\"CitationRef\\\"\\u003e21\\u003c/span\\u003e \\u003c/sup\\u003e, and phosphorus trichloride (PCl₃)\\u003csup\\u003e \\u003cspan citationid=\\\"CR22\\\" class=\\\"CitationRef\\\"\\u003e22\\u003c/span\\u003e \\u003c/sup\\u003e introduces additional complexity. These additives can produce harmful gases and further complicate the reaction process\\u003csup\\u003e \\u003cspan citationid=\\\"CR23\\\" class=\\\"CitationRef\\\"\\u003e23\\u003c/span\\u003e \\u003c/sup\\u003e. Clearly, the current thermocatalytic strategies in industrial ester production face significant challenges.\\u003c/p\\u003e \\u003cp\\u003eTo address these challenges, Yoshio Hisaeda and Hisashi Shimakoshi proposed a photocatalytic process for acyl chloride generation, utilizing the dechlorination of trichloromethyl compounds, thereby eliminating the need for acylating agents (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig1\\\" class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003ec)\\u003csup\\u003e\\u003cspan citationid=\\\"CR24\\\" class=\\\"CitationRef\\\"\\u003e24\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR25\\\" class=\\\"CitationRef\\\"\\u003e25\\u003c/span\\u003e\\u003c/sup\\u003e. This innovative approach offers significant advantages for ester production, particularly by overcoming the detrimental aspects of traditional thermocatalytic methods. However, the industrial application of photocatalysis is still constrained by the low energy utilization efficiency, difficulties in catalyst separation, and slow reaction kinetics\\u003csup\\u003e\\u003cspan citationid=\\\"CR26\\\" class=\\\"CitationRef\\\"\\u003e26\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR27\\\" class=\\\"CitationRef\\\"\\u003e27\\u003c/span\\u003e\\u003c/sup\\u003e.\\u003c/p\\u003e \\u003cp\\u003eIn recent years, electrocatalysis has emerged as a promising strategy for synthesizing value-added compounds due to its high reactivity, controllable selectivity, mild reaction conditions, environmental friendliness, and scalability (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig1\\\" class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003ed)\\u003csup\\u003e\\u003cspan additionalcitationids=\\\"CR29\\\" citationid=\\\"CR28\\\" class=\\\"CitationRef\\\"\\u003e28\\u003c/span\\u003e\\u0026ndash;\\u003cspan citationid=\\\"CR30\\\" class=\\\"CitationRef\\\"\\u003e30\\u003c/span\\u003e\\u003c/sup\\u003e. However, acyl chloride synthesis from trichloromethyl compounds through the electrochemical method is challenging. The cathodic process of electrochemical reduction trichloromethyl compounds involves three types of reactions (dechlorination, hydrogenation, and oxygen reduction reaction (ORR)). Conventional path is prone to the coupling of progressive dechlorination and hydrogenation steps (i.e., hydrodechlorination, \\u003cb\\u003ePath 1, Supplementary Figs.\\u0026nbsp;1\\u003c/b\\u003e), typically resulting in a mixture of hydrodechlorination products\\u003csup\\u003e\\u003cspan citationid=\\\"CR31\\\" class=\\\"CitationRef\\\"\\u003e31\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR32\\\" class=\\\"CitationRef\\\"\\u003e32\\u003c/span\\u003e\\u003c/sup\\u003e. Undoubtedly, the synthesis of acyl chloride requires switch from the hydrodechlorination process to the coupling of dechlorination and oxygenation (\\u003cb\\u003ePath 2, Supplementary Figs.\\u0026nbsp;1 and note 1\\u003c/b\\u003e). How to obtain reactive oxygen species (ROSs) and prioritize oxygen insertion step has become crucial. Regrettably, to date, studies on the electrochemical method for acyl chloride synthesis remain sparse, let alone ascertaining the reaction mechanism and the influence factors of interlaced coupling of possible electrochemical reduction steps.\\u003c/p\\u003e \\u003cp\\u003e \\u003c/p\\u003e \\u003cp\\u003eHere, we propose an oxygen (O₂)-triggered electrochemical process for acyl chloride generation, followed by cascading with chemical nucleophilic reaction for the highly selective synthesis of esters (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig1\\\" class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003ed). Using 2-chloro-5-trichloromethyl pyridine (TCMP) as a model reaction substrate, under continuous O\\u003csub\\u003e2\\u003c/sub\\u003e supply in tetrabutylammonium tetrafluoroborate (TBAT) solution using CH\\u003csub\\u003e3\\u003c/sub\\u003eOH as solvent, the O₂ insertion behavior over the activated Ag electrode is achieved during the electrochemical process \\u003cem\\u003evia\\u003c/em\\u003e ROSs of oxygen reduction reaction (ORR) coupling with dechlorination intermediate. The generation of ROSs is thermodynamically more favorable than active hydrogen production by hydrogen evolution reaction (HER), thereby shifting the reaction pathway from the conventional stepwise hydrodechlorination to the formation of 6-chloronicotinoyl chloride (CNC). As a result, superior performance for MCN synthesis was achieved with 93.2% of high selectivity, 92.5% of yield, and excellent cycling stability over the activated Ag electrode at the potential of \\u0026minus;\\u0026thinsp;0.6 V vs Ag/AgCl. Furthermore, the wide substrate scope and excellent performance in flow electrolyzer validate the broad and promising applicability of this electrocatalysis-cascaded chemistry system for esters synthesis.\\u003c/p\\u003e\"},{\"header\":\"Results\",\"content\":\"\\u003cdiv id=\\\"Sec3\\\" class=\\\"Section2\\\"\\u003e \\u003ch2\\u003eDesign of reaction system\\u003c/h2\\u003e \\u003cp\\u003eThe O\\u003csub\\u003e2\\u003c/sub\\u003e-triggered electrochemical-chemical nucleophilic reaction cascaded system is shown in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig2\\\" class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ea. The electrocatalytic product, CNC will be obtained via the substrate TCMP reacted with O\\u003csub\\u003e2\\u003c/sub\\u003e over the activated Ag mesh (Ag\\u003csub\\u003e(a)\\u003c/sub\\u003e) electrode, then quickly converted to MCN by chemical nucleophilic reaction. Both electrolytic synthesis of CNC and subsequent chemical nucleophilic reaction to generate MCN occur in the cathode chamber of the electrolytic cell. In detail, a continuous flow of O\\u003csub\\u003e2\\u003c/sub\\u003e is pumped into CH\\u003csub\\u003e3\\u003c/sub\\u003eOH solution containing TCMP as the substrate and TBAT as the electrolyte in the cathode electrolysis system. The purpose of using these solvents and electrolytes is forming the organic environment for electrolysis, which is more difficult to ionize than aqueous solution, resulting in minimize the occurrence of HER as much as possible. Of course, CH\\u003csub\\u003e3\\u003c/sub\\u003eOH not only acts as a solvent but also drives nucleophilic reactions towards a more favorable direction for synthesizing MCN. In fact, continuous O\\u003csub\\u003e2\\u003c/sub\\u003e supply is a very important step. The pumped O\\u003csub\\u003e2\\u003c/sub\\u003e as mainly oxygen source is first reduced to ROSs (i.e., O*) over the Ag\\u003csub\\u003e(a)\\u003c/sub\\u003e) electrode, which can directly react with the dechlorinated intermediate of TCMP.\\u003c/p\\u003e \\u003cp\\u003eThe Ag\\u003csub\\u003e(a)\\u003c/sub\\u003e electrode is specifically chosen as the cathode because of its high activity for electrochemical dechlorination and ease of ORR reaction at low overpotential. The preparation of the Ag\\u003csub\\u003e(a)\\u003c/sub\\u003e electrode through the electrochemical cyclic voltammetry (CV) activation treatments has been reported in our previous research\\u003csup\\u003e\\u003cspan citationid=\\\"CR33\\\" class=\\\"CitationRef\\\"\\u003e33\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR34\\\" class=\\\"CitationRef\\\"\\u003e34\\u003c/span\\u003e\\u003c/sup\\u003e. The crystallographic structures, microstructures, and chemical states were probed by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy (XPS) (\\u003cb\\u003eSupplementary Figs.\\u0026nbsp;2\\u0026ndash;8, Tables\\u0026nbsp;1\\u0026ndash;2, and notes 2\\u0026ndash;7\\u003c/b\\u003e). Compared to the Ag without activation, Ag\\u003csub\\u003e(a)\\u003c/sub\\u003e exhibits rougher surface with nanoscale clusters and lower valence state, resulting in larger active specific surface area and enhanced site activity for dechlorination\\u003csup\\u003e\\u003cspan citationid=\\\"CR35\\\" class=\\\"CitationRef\\\"\\u003e35\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR36\\\" class=\\\"CitationRef\\\"\\u003e36\\u003c/span\\u003e\\u003c/sup\\u003e.\\u003c/p\\u003e \\u003cp\\u003e \\u003c/p\\u003e \\u003c/div\\u003e\\n\\u003ch3\\u003eO-triggered electrocatalytic dechlorination cascaded with chemical reaction\\u003c/h3\\u003e\\n\\u003cp\\u003eLinear sweep voltammetry (LSV) was measured under different atmospheres with or without TCMP (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig2\\\" class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003eb). In an anaerobic environment (N\\u003csub\\u003e2\\u003c/sub\\u003e), no significant current can be observed when TCMP is absent in solution (yellow dotted line). The increase of current with an onset potential of \\u0026minus;\\u0026thinsp;0.15 V after adding TCMP indicates the electrochemical reduction of TCMP (yellow solid line). Upon pumping of O\\u003csub\\u003e2\\u003c/sub\\u003e, the apparently increased current and positively shifted onset potential (0.07 V) can be seen (blue dotted line), suggesting that O\\u003csub\\u003e2\\u003c/sub\\u003e participates in the electrochemical reductive reaction (oxygen reduction reaction, ORR) with a low overpotential. Further, a higher current can be obtained after adding TCMP (blue solid line), implying simultaneous ORR and dechloridation. For further studying the behavior of increased current in O\\u003csub\\u003e2\\u003c/sub\\u003e involved reaction, a series of electrolytic experiments were conducted under various environments. TCMP and products (CCMP, CMP, MCN, CNA) were quantified by high-performance liquid chromatography (HPLC) according to the corresponding calibration curves (\\u003cb\\u003eSupplementary Fig.\\u0026nbsp;9\\u003c/b\\u003e). DCMP was detected by liquid chromatography-mass spectrometry (LCMS) in \\u003cb\\u003eSupplementary Fig.\\u0026nbsp;10\\u003c/b\\u003e. As shown in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig2\\\" class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ec, in N\\u003csub\\u003e2\\u003c/sub\\u003e-saturated CH\\u003csub\\u003e3\\u003c/sub\\u003eOH solution using TBAT as an electrolyte, only hydrodechlorination products (5.2% of DCMP, 2.0% of CCMP, and 3.8% of CMP) of \\u003cb\\u003ePath 1\\u003c/b\\u003e can be detected. In contrast, in the situation of O\\u003csub\\u003e2\\u003c/sub\\u003e saturation, the majority of products (92.5% of MCN, and 3.0% of CNA) belong to the oxygenation-dechlorination products in \\u003cb\\u003ePath 2\\u003c/b\\u003e. Combined with the result in the mixed gas (O\\u003csub\\u003e2\\u003c/sub\\u003e/N\\u003csub\\u003e2\\u003c/sub\\u003e, 20/80) further confirms the decisive effect of O\\u003csub\\u003e2\\u003c/sub\\u003e for route switching (\\u003cb\\u003eSupplementary Fig.\\u0026nbsp;11\\u003c/b\\u003e and \\u003cb\\u003enote 8\\u003c/b\\u003e). Meanwhile, the addition of O\\u003csub\\u003e2\\u003c/sub\\u003e distinctly improves the conversion (from 11.0\\u0026ndash;99.2% in CH\\u003csub\\u003e3\\u003c/sub\\u003eOH solution with TBAT). Additionally, this O\\u003csub\\u003e2\\u003c/sub\\u003e-switched phenomenon can be also seen when changing solvent (from CH\\u003csub\\u003e3\\u003c/sub\\u003eOH to CH\\u003csub\\u003e3\\u003c/sub\\u003eCN in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig2\\\" class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ec) and electrolyte (from TBAT to LiOAc in \\u003cb\\u003eSupplementary Fig.\\u0026nbsp;12\\u003c/b\\u003e and \\u003cb\\u003enote 9\\u003c/b\\u003e). Assuredly, compared with solvent and electrolyte, the presence of O\\u003csub\\u003e2\\u003c/sub\\u003e plays a determining role in the choice of electrochemical pathways. Notably, solvent and electrolyte also have effect on the subsequent chemical reaction. As shown in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig2\\\" class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ec, only CNA can be seen as the oxygenation-dechlorination product when using CH\\u003csub\\u003e3\\u003c/sub\\u003eCN as solvent in the presence of O\\u003csub\\u003e2\\u003c/sub\\u003e, verifying the subsequent chemical reaction for MCN formation using CH\\u003csub\\u003e3\\u003c/sub\\u003eOH as nucleophile. The source of CNA may be attributed to the inevitable H\\u003csub\\u003e2\\u003c/sub\\u003eO in the solution or produced by ORR, which is explained by a series of electrochemical measurements in \\u003cb\\u003eSupplementary Fig.\\u0026nbsp;13\\u003c/b\\u003e and \\u003cb\\u003eNote 10\\u003c/b\\u003e. Further, the substrate and products over time under various electrolytic environments are shown in \\u003cb\\u003eSupplementary Fig.\\u0026nbsp;14\\u003c/b\\u003e and \\u003cb\\u003enote 11\\u003c/b\\u003e.\\u003c/p\\u003e \\u003cp\\u003eThe effect of potential under different atmosphere conditions was further investigated (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig2\\\" class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ed and \\u003cb\\u003eSupplementary Fig.\\u0026nbsp;15\\u003c/b\\u003e). In saturated-O\\u003csub\\u003e2\\u003c/sub\\u003e situation, the conversion of TCMP and yield of MCN present sharp growing trend with the increasing the cathodic potential from 0 to \\u0026minus;\\u0026thinsp;0.6 V, and then maintain the steady values from \\u0026minus;\\u0026thinsp;0.6 to \\u0026minus;\\u0026thinsp;1.4 V. The optimal conversion (99.2%) of TCMP and yield of MCN (92.5%) can be found at the potential of \\u0026minus;\\u0026thinsp;0.6 V. In saturated-N\\u003csub\\u003e2\\u003c/sub\\u003e situation, although an increase of TCMP conversion can be obtained with the increasing of potential (from 0 to \\u0026minus;\\u0026thinsp;1.4 V), the highest conversion is only 49.0% at \\u0026minus;\\u0026thinsp;1.4 V, showing the lower reactivity compared with the reaction in saturated-O\\u003csub\\u003e2\\u003c/sub\\u003e situation. Meanwhile, potential also affects the selectivity of dechlorination products, and the yield of CMP increases with potential increasing, which is owing to the acceleration of stepwise dechlorination (\\u003cb\\u003eSupplementary Table S3\\u003c/b\\u003e). In addition, the O\\u003csub\\u003e2\\u003c/sub\\u003e-participated reaction begins at an earlier potential (\\u0026minus;\\u0026thinsp;0.2 V) in contrast to that of hydrodechlorination process (\\u0026minus;\\u0026thinsp;0.4 V), indicating that this reaction is more favorable. The electrolysis result in the mixed gas (O\\u003csub\\u003e2\\u003c/sub\\u003e/N\\u003csub\\u003e2\\u003c/sub\\u003e, 20/80) environment shown in \\u003cb\\u003eSupplementary Fig.\\u0026nbsp;15\\u003c/b\\u003e confirms that a more negative potential may promote the production of hydrodechlorination products in the case of insufficient O\\u003csub\\u003e2\\u003c/sub\\u003e, causing the competition of \\u003cb\\u003ePath 1\\u003c/b\\u003e.\\u003c/p\\u003e \\u003cp\\u003ePotential-dependent Bode phase plots were employed to disclose the \\u003cem\\u003ein-situ\\u003c/em\\u003e interfacial reaction properties (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig2\\\" class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ee, \\u003cb\\u003eSupplementary Fig.\\u0026nbsp;16\\u003c/b\\u003e). Under the condition of without TCMP in N\\u003csub\\u003e2\\u003c/sub\\u003e, the peak at the low and medium frequency region begins to sharply decrease at \\u0026minus;\\u0026thinsp;0.8 V, indicating the occurrence of hydrogen evolution reaction (HER). After adding TCMP, the amplitude of the phase angle decreased, and the peak at \\u0026minus;\\u0026thinsp;0.2 V rapidly decreased, suggesting the start of TCMP reduction with fast charge transfer. Moreover, the negative shift of peak can be seen from \\u0026minus;\\u0026thinsp;0.6 to \\u0026minus;\\u0026thinsp;1.4 V, signifying the stepwise hydrodechlorination process. Without TCMP in O\\u003csub\\u003e2\\u003c/sub\\u003e-saturated atmosphere (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig2\\\" class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ee), the distinct decrease of the phase angle amplitude at \\u0026minus;\\u0026thinsp;0.2 V suggesting the occurrence of ORR reaction, which is consistent with the LSV results. Obviously, a more negative potential is needed for HER (\\u0026minus;\\u0026thinsp;0.8 V) than ORR (\\u0026minus;\\u0026thinsp;0.2 V), demonstrating ORR is more likely to occur than HER. The above result explains the importance of the thermodynamically preferred ORR to the pathway switch. After adding TCMP (\\u003cb\\u003eSupplementary Fig.\\u0026nbsp;13c\\u003c/b\\u003e), the disappearance of the negatively shifted peak implies that the stepwise hydrodechlorination vanishes and is replaced by the ORR-coupled dechlorination process.\\u003c/p\\u003e \\u003cp\\u003eThe electrode-solution interface microenvironment, regulating by electrolyte, plays a vital role in selectivity of products. Hence, the influence of electrolytes (concentration and variety) on the selectivity of MCN was evaluated in O\\u003csub\\u003e2\\u003c/sub\\u003e-saturated CH\\u003csub\\u003e3\\u003c/sub\\u003eOH solution. The selectivity of MCN increases with the decrease of electrolyte concentration, and the degree of this trend is dominated by electrolyte variety (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig2\\\" class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ef \\u003cb\\u003eand Supplementary Table\\u0026nbsp;4\\u003c/b\\u003e). TBAT and tetrabutylammonium bromide (TBAB) exhibit comparatively higher and more stable selectivity (73.3\\u0026thinsp;~\\u0026thinsp;93.7% and 75.1\\u0026thinsp;~\\u0026thinsp;85.3%, respectively) compared with other four electrolytes. To explain these phenomena, the conversion and yield distribution in different concentrations of electrolytes are analyzed (\\u003cb\\u003eSupplementary Fig.\\u0026nbsp;17, 18\\u003c/b\\u003e and \\u003cb\\u003enote 12\\u003c/b\\u003e). On the whole, the increased electrolyte concentration promotes the competitive reactions (hydrodechlorination in in TBAT, TBAB, LiClO\\u003csub\\u003e4\\u003c/sub\\u003e, LiOAc and LiOAc\\u0026middot;2H\\u003csub\\u003e2\\u003c/sub\\u003eO, and self-coupling reaction in TMAH) in electrocatalysis process to varying degrees, resulting in the decline of MCN selectivity in overall products. Second, it can also influence the selectivity in chemical reactions by investigating the MCN selectivity in \\u003cb\\u003ePath 2\\u003c/b\\u003e (Sel.\\u003csub\\u003eMCN\\u003c/sub\\u003e(Path2)) obtained by the electrochemical reaction starting from TCMP and the chemical reaction starting from theoretically equimolar CNC (\\u003cb\\u003eSupplementary Fig.\\u0026nbsp;19\\u003c/b\\u003e and \\u003cb\\u003enote 13\\u003c/b\\u003e). To elucidate the correlation between electrolyte and selectivity of MCN in \\u003cb\\u003ePath 2\\u003c/b\\u003e, the solution pH under different variety and concentration of electrolytes was measured (\\u003cb\\u003eSupplementary Tables\\u0026nbsp;5 and 6\\u003c/b\\u003e). As depicted in \\u003cb\\u003eSupplementary Fig.\\u0026nbsp;20\\u003c/b\\u003e, the acidic environment is conducive to the formation of MCN with high selectivity and the selectivity of MCN decreases with pH increasing.\\u003c/p\\u003e \\u003cp\\u003eBased on the above results, the optimal performance with conversion of 99.2%, yield of 92.5%, and selectivity of 93.2% for MCN production can be obtained at the potential of \\u0026minus;\\u0026thinsp;0.6 V in 0.03 M TBAT solution using CH\\u003csub\\u003e3\\u003c/sub\\u003eOH as solvent under continuous O\\u003csub\\u003e2\\u003c/sub\\u003e feeding. The durability was evaluated by performing 30 consecutive cyclic tests (180 h). As shown in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig2\\\" class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003eg, the yield and selectivity of MCN remain at ~\\u0026thinsp;90.8 and 93.4%, respectively, manifesting the excellent outstanding reusability and stability of this system. The four electrons transferred Faradaic efficiency (FE) with ~\\u0026thinsp;44.1% can be seen, and the number of electrons transferred to form MCN is calculated by *O formation. The remaining electrons can be used for the production of other ROSs in ORR, which is possible to produce MCN. FE calculated by ROSs using different numbers of electrons are recorded in \\u003cb\\u003eSupplementary Note 14\\u003c/b\\u003e. The Ag\\u003csub\\u003e(a)\\u003c/sub\\u003e electrode after electrocatalysis for 30 cycles was characterized by SEM and XPS (\\u003cb\\u003eSupplementary Figs.\\u0026nbsp;21 and 22\\u003c/b\\u003e), revealing the high durability. Moreover, a technoeconomic analysis (TEA) on the plant-gate levelized costs was performed to evaluate the profitability of this technology\\u003csup\\u003e \\u003cspan additionalcitationids=\\\"CR38\\\" citationid=\\\"CR37\\\" class=\\\"CitationRef\\\"\\u003e37\\u003c/span\\u003e\\u0026ndash;\\u003cspan citationid=\\\"CR39\\\" class=\\\"CitationRef\\\"\\u003e39\\u003c/span\\u003e \\u003c/sup\\u003e, and the details of TEA are available in \\u003cb\\u003eSupplementary Fig.\\u0026nbsp;23\\u003c/b\\u003e and \\u003cb\\u003eNote 15\\u003c/b\\u003e. Figure\\u0026nbsp;\\u003cspan refid=\\\"Fig2\\\" class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003eh shows the profitable regions for MCN generation as a function of FE and electricity cost. The calculations indicate a profit of 2328.3 US\\u003cspan\\u003e$\\u003c/span\\u003e per ton can be seen for MCN generation using this system as shown in the marked star. Even with a relatively high electricity price (0.2 \\u003cspan\\u003e$\\u003c/span\\u003e kW h\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e), this technology still shows the good economic benefits, suggesting the promising potential in practical production. Furthermore, by regulating the electrolyte, atmosphere and potential conditions, the other products, CMP and CNA with high selectivity of 99.4 and 96.1%, respectively, were achieved (\\u003cb\\u003eSupplementary Figs.\\u0026nbsp;24 and 25\\u003c/b\\u003e).\\u003c/p\\u003e\\n\\u003ch3\\u003eMechanistic studies\\u003c/h3\\u003e\\n\\u003cp\\u003eElectrochemical \\u003cem\\u003ein-situ\\u003c/em\\u003e characterizations were conducted to monitor some key intermediates. As depicted in \\u003cem\\u003ein-situ\\u003c/em\\u003e Raman spectra (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig3\\\" class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003ea), the characteristic peaks of oxygen intermediate at 1050 and 1150 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e attributed to the adsorbed intermediates species (*OH and *O\\u003csub\\u003e2\\u003c/sub\\u003e) on the surface of catalyst\\u003csup\\u003e\\u003cspan additionalcitationids=\\\"CR41\\\" citationid=\\\"CR40\\\" class=\\\"CitationRef\\\"\\u003e40\\u003c/span\\u003e\\u0026ndash;\\u003cspan citationid=\\\"CR42\\\" class=\\\"CitationRef\\\"\\u003e42\\u003c/span\\u003e\\u003c/sup\\u003e, respectively, imply the occurrence of ORR (O\\u003csub\\u003e2\\u003c/sub\\u003e + * \\u0026rarr; *O\\u003csub\\u003e2\\u003c/sub\\u003e, *O\\u003csub\\u003e2\\u003c/sub\\u003e\\u0026thinsp;+\\u0026thinsp;H\\u003csup\\u003e+\\u003c/sup\\u003e + e\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e \\u0026rarr; *OOH, *OOH\\u0026thinsp;+\\u0026thinsp;H\\u003csup\\u003e+\\u003c/sup\\u003e + e\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e \\u0026rarr; *O\\u0026thinsp;+\\u0026thinsp;H\\u003csub\\u003e2\\u003c/sub\\u003eO, *O\\u0026thinsp;+\\u0026thinsp;H\\u003csup\\u003e+\\u003c/sup\\u003e + e\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e \\u0026rarr; *OH, *OH\\u0026thinsp;+\\u0026thinsp;H\\u003csup\\u003e+\\u003c/sup\\u003e + e\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e \\u0026rarr; H\\u003csub\\u003e2\\u003c/sub\\u003eO)\\u003csup\\u003e\\u003cspan additionalcitationids=\\\"CR44\\\" citationid=\\\"CR43\\\" class=\\\"CitationRef\\\"\\u003e43\\u003c/span\\u003e\\u0026ndash;\\u003cspan citationid=\\\"CR45\\\" class=\\\"CitationRef\\\"\\u003e45\\u003c/span\\u003e\\u003c/sup\\u003e. The increasing intensity of peaks in potential-dependent \\u003cem\\u003ein-situ\\u003c/em\\u003e Raman spectra manifest ORR starts at the potential of \\u0026minus;\\u0026thinsp;0.2 V, in accordance with LSV and electrolytic results (\\u003cb\\u003eSupplementary Fig.\\u0026nbsp;26\\u003c/b\\u003e). Two peaks located at 1450 and 1650 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e are corresponding to C-Cl bonds of TCMP. The C-Cl bond at 1450 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e appears later (about 0.3 V) than that at 1650 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e with the increasing potential, suggesting the stepwise dechloridation (\\u003cb\\u003eSupplementary Fig.\\u0026nbsp;27\\u003c/b\\u003e)\\u003csup\\u003e\\u003cspan citationid=\\\"CR46\\\" class=\\\"CitationRef\\\"\\u003e46\\u003c/span\\u003e\\u003c/sup\\u003e. The simultaneous appearance of characteristic peaks ascribed to dechloridation and ORR in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig3\\\" class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003eb confirms the coupled reaction\\u003csup\\u003e\\u003cspan citationid=\\\"CR37\\\" class=\\\"CitationRef\\\"\\u003e37\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR47\\\" class=\\\"CitationRef\\\"\\u003e47\\u003c/span\\u003e\\u003c/sup\\u003e. In the presence of O\\u003csub\\u003e2\\u003c/sub\\u003e, the earlier initiation of ORR than dechlorination leads to a switch from single hydrodechlorination to ORR-coupled dechlorination reaction. Time-dependent \\u003cem\\u003ein-situ\\u003c/em\\u003e Raman spectra at the potential of \\u0026minus;\\u0026thinsp;0.6 V shows the inconspicuous growth of peak at 1450 and 1650 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e, illustrating the C-Cl bonds are broken continuously (\\u003cb\\u003eSupplementary Fig.\\u0026nbsp;28\\u003c/b\\u003e). Meanwhile, the adsorbed OH and O\\u003csub\\u003e2\\u003c/sub\\u003e at 1050 and 1150 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e also suggest the steady coupling reaction.\\u003c/p\\u003e \\u003cp\\u003e \\u003c/p\\u003e \\u003cp\\u003eFurthermore, the generated products and intermediates were detected \\u003cem\\u003evia in-situ\\u003c/em\\u003e FTIR spectroscopy (\\u003cb\\u003eSupplementary Fig.\\u0026nbsp;29\\u003c/b\\u003e). Under the condition of O\\u003csub\\u003e2\\u003c/sub\\u003e-particapted CH\\u003csub\\u003e3\\u003c/sub\\u003eOH solution, the upward peaks at 1040, 1160, and 1443 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e are attributed to the stretching mode of *O\\u003csub\\u003e2\\u003c/sub\\u003e, OOH*, and *OH, respectively, suggesting the ORR process (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig3\\\" class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003ec and \\u003cb\\u003eSupplementary Fig.\\u0026nbsp;30\\u003c/b\\u003e) \\u003csup\\u003e\\u003cspan citationid=\\\"CR48\\\" class=\\\"CitationRef\\\"\\u003e48\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR49\\\" class=\\\"CitationRef\\\"\\u003e49\\u003c/span\\u003e\\u003c/sup\\u003e. The absorption bands at 1588, and 3450 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e assigned to the bending vibration and stretching mode of O─H affirm the generation of water molecules from ORR \\u003csup\\u003e\\u003cspan citationid=\\\"CR50\\\" class=\\\"CitationRef\\\"\\u003e50\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR51\\\" class=\\\"CitationRef\\\"\\u003e51\\u003c/span\\u003e\\u003c/sup\\u003e. When containing TCMP in solution, C\\u0026thinsp;=\\u0026thinsp;C skeletal vibration of the pyridine ring was observed at 1660 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e, corresponding to the adsorbed TCMP on the electrode surface. The peak at 1240 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e assigned to the stretching band of C-Cl with a tendency of first rising (from 0.2 to \\u0026minus;\\u0026thinsp;0.6 V) and then descend manifests the adsorption and consumption of TCMP. Notably, the weak peak at 1705 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e is the stretching vibration of C\\u0026thinsp;=\\u0026thinsp;O, implying the transient existence of CNC on the surface of electrode. On the other hand, under the condition of N\\u003csub\\u003e2\\u003c/sub\\u003e-pumped CH\\u003csub\\u003e3\\u003c/sub\\u003eOH solution with TCMP, two upward peaks corresponding to CH and CH\\u003csub\\u003e2\\u003c/sub\\u003e observed at 1105 and 1410 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e indicate the formation of new CH/CH\\u003csub\\u003e2\\u003c/sub\\u003e bonds by hydrodechlorination (\\u003cb\\u003eSupplementary Fig.\\u0026nbsp;31\\u003c/b\\u003e)\\u003csup\\u003e\\u003cspan citationid=\\\"CR52\\\" class=\\\"CitationRef\\\"\\u003e52\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR53\\\" class=\\\"CitationRef\\\"\\u003e53\\u003c/span\\u003e\\u003c/sup\\u003e.\\u003c/p\\u003e \\u003cp\\u003e \\u003cem\\u003eIn-situ\\u003c/em\\u003e electron paramagnetic resonance (EPR) spectra were conducted by using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and 5-(deisopropoxyphosphoryl)-5-methyl-1-pyrroline-N-oxide (DIPPMPO) as the radical trapping reagents\\u003csup\\u003e\\u003cspan additionalcitationids=\\\"CR55\\\" citationid=\\\"CR54\\\" class=\\\"CitationRef\\\"\\u003e54\\u003c/span\\u003e\\u0026ndash;\\u003cspan citationid=\\\"CR56\\\" class=\\\"CitationRef\\\"\\u003e56\\u003c/span\\u003e\\u003c/sup\\u003e. As demonstrated in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig3\\\" class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003ed, \\u003cb\\u003eSupplementary Fig.\\u0026nbsp;32\\u003c/b\\u003e and \\u003cb\\u003eNote 16\\u003c/b\\u003e, ROSs (\\u0026bull;OH, \\u0026bull;OOH, and \\u0026bull;O) can be captured by DMPO during the electrocatalytic process, implying the ORR process. No signal of \\u0026bull;H can be seen when using DMPO as trapping reagents, suggesting that hydrogenation process is difficult to occur. The descend of peak intensity of ROSs after the addition of TCMP verifies the consumption of oxygen intermediates. A gradually increased twelve-fold signal with increasing of potential is corresponded to DIPPMPO- \\u0026bull;C, suggesting the activation of TCMP (\\u003cb\\u003eSupplementary Fig.\\u0026nbsp;33\\u003c/b\\u003e). To further distinguish the source of \\u0026bull;C (TCMP or CH\\u003csub\\u003e3\\u003c/sub\\u003eOH), the comparison of EPR spectra was performed. As shown in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig3\\\" class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003ee and \\u003cb\\u003eSupplementary Fig.\\u0026nbsp;34\\u003c/b\\u003e, no signal can be found in the absence of TCMP, whereas the signal becomes stronger with time in presence of TCMP in solution, affirming the captured \\u0026bull;C comes from the activation of TCMP. The above results affirm the concurrence of ORR and dechloridation. Besides, the hydrodechlorination process of \\u003cb\\u003ePath 1\\u003c/b\\u003e is also verified by the distinct nine-fold (1:1:2:1:2:1:2:1:1) signal of *H verify the (\\u003cb\\u003eSupplementary Fig.\\u0026nbsp;35\\u003c/b\\u003e)\\u003csup\\u003e\\u003cspan citationid=\\\"CR57\\\" class=\\\"CitationRef\\\"\\u003e57\\u003c/span\\u003e\\u003c/sup\\u003e. Theoretically, the electrochemical ORR-coupled dechlorination reaction may undergo two paths according to the sequence of dechlorination and oxygen bonding, which can be distinguished by different free radicals (\\u003cb\\u003eSupplementary Fig.\\u0026nbsp;36\\u003c/b\\u003e). As displayed in femtosecond transient absorption spectra (fs-TAS, Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig3\\\" class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003ef)\\u003csup\\u003e\\u003cspan citationid=\\\"CR58\\\" class=\\\"CitationRef\\\"\\u003e58\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR59\\\" class=\\\"CitationRef\\\"\\u003e59\\u003c/span\\u003e\\u003c/sup\\u003e, the enhanced signal at 432 nm confirms the presence of carbene species, illustrating that the mechanism of CNC generation follows a first dechlorination \\u003cem\\u003evia\\u003c/em\\u003e 2e reaction and then oxygen insertion route (C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e3\\u003c/sub\\u003eCl\\u003csub\\u003e4\\u003c/sub\\u003eN* \\u0026rarr; C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e3\\u003c/sub\\u003eCl\\u003csub\\u003e3\\u003c/sub\\u003eN* \\u0026rarr; C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e3\\u003c/sub\\u003eCl\\u003csub\\u003e2\\u003c/sub\\u003eN* \\u0026rarr; C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e3\\u003c/sub\\u003eCl\\u003csub\\u003e2\\u003c/sub\\u003eNO*). Additionally, the transient CNC was detected by LCMS analysis (\\u003cb\\u003eSupplementary Fig.\\u0026nbsp;37\\u003c/b\\u003e).\\u003c/p\\u003e \\u003cp\\u003eIsotope labeling experiments with the assistance of LCMS were carried out to track the oxygen source. As shown in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig3\\\" class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003eg, the peaks with mass-to-charge ratio (\\u003cem\\u003em\\u003c/em\\u003e/\\u003cem\\u003ez\\u003c/em\\u003e) of 159.55 and 173.58 assigned to the signals of C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e5\\u003c/sub\\u003eClNO\\u003csup\\u003e\\u003cspan citationid=\\\"CR18\\\" class=\\\"CitationRef\\\"\\u003e18\\u003c/span\\u003e\\u003c/sup\\u003eO (CNA-\\u003csup\\u003e\\u003cspan citationid=\\\"CR18\\\" class=\\\"CitationRef\\\"\\u003e18\\u003c/span\\u003e\\u003c/sup\\u003eO) and C\\u003csub\\u003e7\\u003c/sub\\u003eH\\u003csub\\u003e7\\u003c/sub\\u003eClNO\\u003csup\\u003e\\u003cspan citationid=\\\"CR18\\\" class=\\\"CitationRef\\\"\\u003e18\\u003c/span\\u003e\\u003c/sup\\u003eO (MCN-\\u003csup\\u003e\\u003cspan citationid=\\\"CR18\\\" class=\\\"CitationRef\\\"\\u003e18\\u003c/span\\u003e\\u003c/sup\\u003eO) fragments, respectively, confirm the participation of O\\u003csub\\u003e2\\u003c/sub\\u003e in the electrochemical process of CNC generation \\u003cem\\u003evia\\u003c/em\\u003e forming C\\u0026thinsp;=\\u0026thinsp;\\u003csup\\u003e18\\u003c/sup\\u003eO bond. Notably, the peaks at \\u003cem\\u003em\\u003c/em\\u003e/\\u003cem\\u003ez\\u003c/em\\u003e of 161.55 corresponded to C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e5\\u003c/sub\\u003eClN\\u003csup\\u003e\\u003cspan citationid=\\\"CR18\\\" class=\\\"CitationRef\\\"\\u003e18\\u003c/span\\u003e\\u003c/sup\\u003eO\\u003csub\\u003e2\\u003c/sub\\u003e indicated that the source of H\\u003csub\\u003e2\\u003c/sub\\u003eO participated in nucleophilic reaction for CNA generation comes from the ORR process. In addition, the chemical nucleophilic reaction for MCN generation was investigated through replacing CH\\u003csub\\u003e3\\u003c/sub\\u003eOH with deuterated CH\\u003csub\\u003e3\\u003c/sub\\u003eOH (CD\\u003csub\\u003e3\\u003c/sub\\u003eOD) solution (\\u003cb\\u003eSupplementary Fig.\\u0026nbsp;38\\u003c/b\\u003e). The appearance of deuterated methyl group verifies CH\\u003csub\\u003e3\\u003c/sub\\u003eOH as the nucleophilic reagent participating in the chemical reaction for MCN generation.\\u003c/p\\u003e \\u003cp\\u003eDensity functional theory (DFT) calculations were conducted to further unravel the effect of intermediates on the reaction mechanism. The free energy diagram for oxygen intermediates along the 2e\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e dechlorination\\u003cem\\u003e-\\u003c/em\\u003eoxygen insertion pathway on Ag (111) are depicted in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig4\\\" class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003ea and \\u003cb\\u003eSupplementary Fig.\\u0026nbsp;39\\u003c/b\\u003e. The elevated energy barrier for C-Cl bond breaking (1.16 and 1.43 eV) indicates the 2e\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e dechlorination is endothermic and the forming of adsorbed carbene (C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e3\\u003c/sub\\u003eCl\\u003csub\\u003e2\\u003c/sub\\u003eN*) is rate-determining step (RDS) in the whole reaction for MCN synthesis, while the adsorption and oxygen insertion processes of oxygen intermediates (O*, OOH*, OH*) are exergonic in free energy, implying the coupling process between carbene and oxygen intermediates are spontaneous. The larger exergonic energy in oxygen insertion processes of O* than those of OOH*, OH* demonstrates O* is more favorable. Moreover, the energy level profile and corresponding adsorption configurations for hydrodechlorination of TCMP are shown in \\u003cb\\u003eSupplementary Figs.\\u0026nbsp;40 and 41\\u003c/b\\u003e, and the less exothermic energy in hydrogenation process (C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e3\\u003c/sub\\u003eCl\\u003csub\\u003e3\\u003c/sub\\u003eN* + H*\\u0026rarr; C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e4\\u003c/sub\\u003eCl\\u003csub\\u003e3\\u003c/sub\\u003eN*, et. al.) than in oxygenation reaction (C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e3\\u003c/sub\\u003eCl\\u003csub\\u003e2\\u003c/sub\\u003eN* + O*\\u0026rarr;C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e3\\u003c/sub\\u003eCl\\u003csub\\u003e2\\u003c/sub\\u003eNO*) in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig4\\\" class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003eb indicates the superior competition of ORR-coupled dechlorination reaction than hydrodechlorination reaction. In the chemical nucleophilic steps for MCN and CNA generation, desorption is the endothermic processes (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig4\\\" class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003ea and \\u003cb\\u003eSupplementary Fig.\\u0026nbsp;42\\u003c/b\\u003e). As depicted in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig4\\\" class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003eb, the endothermic dechlorination process is the RDS for electrocatalytic CNC synthesis. More importantly, the sequence of dechlorination and oxygenation was explored by contrasting free energy steps. The oxygenation-dechlorination process (C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e3\\u003c/sub\\u003eCl\\u003csub\\u003e3\\u003c/sub\\u003eN* \\u0026rarr; C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e3\\u003c/sub\\u003eCl\\u003csub\\u003e2\\u003c/sub\\u003eN* + O*) exhibits lower free energy of RDS (1.48 eV) than that of the oxygenation-dechlorination process (C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e3\\u003c/sub\\u003eCl\\u003csub\\u003e3\\u003c/sub\\u003eNO* \\u0026rarr; C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e3\\u003c/sub\\u003eCl\\u003csub\\u003e2\\u003c/sub\\u003eNO*, 1.81 eV), verifying the route follows first dechlorination and then oxygenation for CNC generation.\\u003c/p\\u003e \\u003cp\\u003eBased on the above investigations, a mechanism of the electrocatalytic ORR\\u0026ndash;coupled dechlorination cascading chemical nucleophilic reaction were proposed, as described in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig4\\\" class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003ec. (Ⅰ) TCMP dechlorination activation: the adsorbed TCMP molecule undergoes twice breaking of C-Cl bonds, and carbene intermediate are formed through 2e\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e process. (Ⅱ) O\\u003csub\\u003e2\\u003c/sub\\u003e activation by ORR: the absorbed O\\u003csub\\u003e2\\u003c/sub\\u003e molecule is reduced by gradually obtaining electrons and protons (produced from anode chamber or CH\\u003csub\\u003e3\\u003c/sub\\u003eOH), and oxygen intermediates are generated by the 4e\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e process (O\\u003csub\\u003e2\\u003c/sub\\u003e \\u0026rarr; OOH* \\u0026rarr; O* \\u0026rarr; OH*). (Ⅲ) CNC is produced through the combination of carbene and oxygen intermediates. (Ⅳ) A chemical nucleophilic reaction happens between CNC and CH\\u003csub\\u003e3\\u003c/sub\\u003eOH to form MCN.\\u003c/p\\u003e \\u003cp\\u003e \\u003c/p\\u003e\\n\\u003ch3\\u003eUniversality of esters production and application of flow electrolyzer\\u003c/h3\\u003e\\n\\u003cp\\u003eThe universality of electrocatalytic ORR-coupled dechlorination cascading chemical reaction of trichloromethyl compounds over Ag\\u003csub\\u003e(a)\\u003c/sub\\u003e electrode was evaluated (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig5\\\" class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003ea, \\u003cb\\u003eSupplementary Fig.\\u0026nbsp;43\\u0026ndash;50\\u003c/b\\u003e, and \\u003cb\\u003eTable\\u0026nbsp;7\\u003c/b\\u003e). Various functionalized substrates containing benzene and pyridine rings reacting with different nucleophilic reagents can be transformed into corresponding esters with high yields (58.8\\u0026thinsp;~\\u0026thinsp;86.4%) and selectivity (69.2\\u0026thinsp;~\\u0026thinsp;100%). To assess the feasibility of this system for practically industrial applications, a two-electrode flow electrolyzer (4 cm\\u003csup\\u003e\\u003cspan citationid=\\\"CR2\\\" class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e) with Ag\\u003csub\\u003e(a)\\u003c/sub\\u003e cathode and carbon paper anode was used for MCN production (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig5\\\" class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003eb and \\u003cb\\u003eSupplementary Fig.\\u0026nbsp;51\\u003c/b\\u003e). The O\\u003csub\\u003e2\\u003c/sub\\u003e-saturated electrolyte containing 20 mM TCMP in 0.03 M TBAT methanol solution was circulated in the flow cell by using a gas-liquid mixed flow pump. The result of constant current electrocatalysis (\\u0026minus;\\u0026thinsp;5 mA cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;2\\u003c/sup\\u003e) in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig5\\\" class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003ec shows a 91.6% of yield and 94.9% of selectivity in 6 h, affirming the superiority and promising utilization of this strategy. Moreover, the results of long-term electrocatalysis for 60 h are displayed in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig5\\\" class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003ed. The sustained voltage (\\u0026minus;\\u0026thinsp;2.2 V), MCN yield rate (8.3 mg h\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;2\\u003c/sup\\u003e), and four electrons transferred FE (48.5%) demonstrate the excellent stability and reusability of Ag\\u003csub\\u003e(a)\\u003c/sub\\u003e electrode.\\u003c/p\\u003e \\u003cp\\u003e \\u003c/p\\u003e\"},{\"header\":\"Conclusion\",\"content\":\"\\u003cp\\u003eIn conclusion, this work presents a highly efficient cascaded approach of electrochemical and chemical reactions for ester production using TCMP as the substrate. The reaction pathway is redirected from conventional hydrodechlorination to the dechlorination-oxygen insertion process by introducing O\\u003csub\\u003e2\\u003c/sub\\u003e. The high reactivity for CNC generation in electrochemical reaction and an acid environment in chemical nucleophilic reaction facilitate a 93.2% selectivity for MCN synthesis. Mechanistic insights suggest that the electrocatalytic process involves an ORR-coupled dechlorination reaction, in which ROSs play a crucial role in generating intermediate CNC. This cascade system of electrochemical and chemical reactions demonstrates excellent performance and scalability, offering a promising alternative to traditional ester production methods, with broad applicability for sustainable industrial processes.\\u003c/p\\u003e \"},{\"header\":\"Methods\",\"content\":\"\\u003ch2\\u003eChemicals and Materials\\u003c/h2\\u003e\\u003cp\\u003eDeionized water and Wahaha water (liquid phase mobile phase only, Hangzhou Wahaha Group CO., Ltd) were used in all the experiments, and deionized water was prepared by the reverse osmosis deionized water machine (Hitech Instruments CO., Ltd) in laboratory. Ag net (100-mesh, 99.99%), Cu net (100-mesh, 99.99%), and Co plate (99.99%) were purchased from Qinghe Yuqian Metal Materials Co., Ltd.\\u003c/p\\u003e\\u003cp\\u003ePhosphoric acid (H\\u003csub\\u003e3\\u003c/sub\\u003ePO\\u003csub\\u003e4\\u003c/sub\\u003e, ≥ 85%), nitric acid (HNO\\u003csub\\u003e3\\u003c/sub\\u003e, 65.0–68.0%), hydrofluoric acid (HF, ≥ 40.0%), hydrochloric acid (HCl, 36.0 ~ 38.0%), sulfuric acid (H\\u003csub\\u003e2\\u003c/sub\\u003eSO\\u003csub\\u003e4\\u003c/sub\\u003e, 95.0 ~ 98.0%), methanol anhydrous (CH\\u003csub\\u003e3\\u003c/sub\\u003eOH, ≥ 99.7%), ethanol absolute (C\\u003csub\\u003e2\\u003c/sub\\u003eH\\u003csub\\u003e5\\u003c/sub\\u003eOH, ≥ 99.7%), acetonitrile (CH\\u003csub\\u003e3\\u003c/sub\\u003eCN, ≥ 99.5%), hydrogen peroxide aqueous solution (H\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e2\\u003c/sub\\u003e, ≥ 30%), and ammonium fluoride (NH\\u003csub\\u003e4\\u003c/sub\\u003eF, ≥ 96.0%) were purchased from Sinopharm Chemical Reagent Co., Ltd (SCR). Methyl alcohol (CH\\u003csub\\u003e3\\u003c/sub\\u003eOH, 99.9%) and acetonitrile (CH\\u003csub\\u003e3\\u003c/sub\\u003eCN, 99.9%) were purchased from Tedia Company, Inc. Lithium acetate dihydrate (LiOAc·2H\\u003csub\\u003e2\\u003c/sub\\u003eO, 99%), lithium acetate (LiOAc, 99.99%), 6-chloronicotinic acid (C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e4\\u003c/sub\\u003eClNO\\u003csub\\u003e2\\u003c/sub\\u003e, CNA, 98%), 2-chloro-5-(trichloromethyl)pyridine (C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e3\\u003c/sub\\u003eCl\\u003csub\\u003e4\\u003c/sub\\u003eN, TCMP, 98%), and 2-chlorobenzotrichloride (C\\u003csub\\u003e7\\u003c/sub\\u003eH\\u003csub\\u003e4\\u003c/sub\\u003eCl\\u003csub\\u003e4\\u003c/sub\\u003e, ≥ 95%) were purchased from Shanghai Macklin Biochemical Co., Ltd (MACKLIN). Methyl 6-chloronicotinate (C\\u003csub\\u003e7\\u003c/sub\\u003eH\\u003csub\\u003e6\\u003c/sub\\u003eClNO\\u003csub\\u003e2\\u003c/sub\\u003e, MCN, 99%), α,α,α,α',α',α'-hexachloro-p-xylene (C\\u003csub\\u003e8\\u003c/sub\\u003eH\\u003csub\\u003e4\\u003c/sub\\u003eCl\\u003csub\\u003e6\\u003c/sub\\u003e, 98%), dimethyl terephthalate (C\\u003csub\\u003e10\\u003c/sub\\u003eH\\u003csub\\u003e10\\u003c/sub\\u003eO\\u003csub\\u003e4\\u003c/sub\\u003e, 99%), 4-fluorobenzotrichloride (C\\u003csub\\u003e7\\u003c/sub\\u003eH\\u003csub\\u003e4\\u003c/sub\\u003eCl\\u003csub\\u003e3\\u003c/sub\\u003eF, 98%), methyl 2-chloropyridine-3-carboxylate (C\\u003csub\\u003e7\\u003c/sub\\u003eH\\u003csub\\u003e6\\u003c/sub\\u003eClNO\\u003csub\\u003e2\\u003c/sub\\u003e, 99.9%), and methanol d4 (CD\\u003csub\\u003e3\\u003c/sub\\u003eOD, 99.8%) were purchased from Meryer Chemical Technology Co., Ltd (MERYER). Methyl benzoate (C\\u003csub\\u003e8\\u003c/sub\\u003eH\\u003csub\\u003e8\\u003c/sub\\u003eO\\u003csub\\u003e2\\u003c/sub\\u003e, \\u0026gt; 99.5%), methyl 2-chlorobenzoate (C\\u003csub\\u003e8\\u003c/sub\\u003eH\\u003csub\\u003e7\\u003c/sub\\u003eClO\\u003csub\\u003e2\\u003c/sub\\u003e, \\u0026gt; 98.0%), tetrabutylammonium tetrafluoroborate (C\\u003csub\\u003e16\\u003c/sub\\u003eH\\u003csub\\u003e36\\u003c/sub\\u003eBF\\u003csub\\u003e4\\u003c/sub\\u003eN, TBAT, ≥ 98.0%), tetramethylammonium hydroxide ((CH\\u003csub\\u003e3\\u003c/sub\\u003e)\\u003csub\\u003e4\\u003c/sub\\u003eNOH, TMAH, 25%), 6-chloronicotinoyl chloride (C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e3\\u003c/sub\\u003eCl\\u003csub\\u003e2\\u003c/sub\\u003eNO, CNC, 98%), lithium perchlorate (LiClO\\u003csub\\u003e4\\u003c/sub\\u003e, 99.99%), and tetrabutylammonium bromide (C\\u003csub\\u003e16\\u003c/sub\\u003eH\\u003csub\\u003e36\\u003c/sub\\u003eBrN, TBAB, 99.0%) were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd (aladdin). Trichlorotoluene (C\\u003csub\\u003e7\\u003c/sub\\u003eH\\u003csub\\u003e5\\u003c/sub\\u003eCl\\u003csub\\u003e3\\u003c/sub\\u003e, \\u0026gt; 99.0%) were purchased from Tokyo Chemical Industry Co., Ltd. Ethyl 6-chloropyridine 3-carboxylate (C\\u003csub\\u003e8\\u003c/sub\\u003eH\\u003csub\\u003e8\\u003c/sub\\u003eClNO\\u003csub\\u003e2\\u003c/sub\\u003e, \\u0026gt; 97%), methyl 6-chloropyridine-2-carboxylate (C\\u003csub\\u003e7\\u003c/sub\\u003eH\\u003csub\\u003e6\\u003c/sub\\u003eClNO\\u003csub\\u003e2\\u003c/sub\\u003e, ≥ 98%), and methyl 4-chlorobenzoate (C\\u003csub\\u003e14\\u003c/sub\\u003eH\\u003csub\\u003e11\\u003c/sub\\u003eClO\\u003csub\\u003e2\\u003c/sub\\u003e, ≥ 98%) were purchased from Accela ChemBio Co., Ltd (Accela). 2-Chloro-6-(trichloromethyl)pyridine (C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e3\\u003c/sub\\u003eCl\\u003csub\\u003e4\\u003c/sub\\u003eN, 99.0%), and 2-chloro-5-methyloyridine (C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e6\\u003c/sub\\u003eClN, CMP 98.38%) were purchased from Bide Pharmatech Co., Ltd. 2-Chloro-3-(trichloromethyl)pyridine (C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e3\\u003c/sub\\u003eF\\u003csub\\u003e4\\u003c/sub\\u003eN, 97%) was purchased from Shanghai Yuanye Bio-Technology Co., Ltd. 4-Chlorobenzotrichloride (C\\u003csub\\u003e7\\u003c/sub\\u003eH\\u003csub\\u003e4\\u003c/sub\\u003eCl\\u003csub\\u003e4\\u003c/sub\\u003e, 98%) was purchased from Shanghai Adamas Reagent Co., Ltd (Damas-beta). Methyl 4-fluorobenzoate (C\\u003csub\\u003e8\\u003c/sub\\u003eH\\u003csub\\u003e7\\u003c/sub\\u003eFO\\u003csub\\u003e2\\u003c/sub\\u003e, 99%) was purchased from J\\u0026amp;K Scientific Co., Ltd. 2-Chloro-5-chloromethylpyridine (C\\u003csub\\u003e6\\u003c/sub\\u003eH\\u003csub\\u003e6\\u003c/sub\\u003eClN, CCMP, 98%) was purchased from Shanghai URChem Ltd. Ethyl 6-chloropyridine-2-carboxylate (C\\u003csub\\u003e8\\u003c/sub\\u003eH\\u003csub\\u003e8\\u003c/sub\\u003eClNO\\u003csub\\u003e2\\u003c/sub\\u003e, 97%) and ethyl 2-chloropyridine-3-carboxylate (C\\u003csub\\u003e8\\u003c/sub\\u003eH\\u003csub\\u003e8\\u003c/sub\\u003eClNO\\u003csub\\u003e2\\u003c/sub\\u003e, 98%) was purchased from Shanghai Yi En Chemical Technology Co., Ltd. Isotopic Oxygen-\\u003csup\\u003e\\u003cspan citationid=\\\"CR18\\\" class=\\\"CitationRef\\\"\\u003e18\\u003c/span\\u003e\\u003c/sup\\u003eO\\u003csub\\u003e2\\u003c/sub\\u003e (≥ 99%) was purchased from Wuhan Isotope Technology Co., Ltd. Except noted, all chemicals were used without further purification.\\u003c/p\\u003e\\u003ch3\\u003ePreparation of catalysts\\u003c/h3\\u003e\\u003ch2\\u003eAg\\u003csub\\u003e(a)\\u003c/sub\\u003e electrode\\u003c/h2\\u003e\\u003cp\\u003eThe activated Ag electrode (Ag\\u003csub\\u003e(a)\\u003c/sub\\u003e) was prepared through the electrochemical cyclic voltammetry (CV) activation treatments. Initially, a 1 × 2 cm\\u003csup\\u003e\\u003cspan citationid=\\\"CR2\\\" class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e piece of Ag mesh was ultrasonicated sequentially in ethanol and deionized water for 10 min to remove surface impurities. Then, the CV process was conducted in an undivided cell containing 1 M HCl solution. The platinum plate, washed Ag mesh and saturated calomel electrode (SCE) were used as the counter electrode, working electrode, and reference electrode, respectively. Specifically, the washed mesh net was activated in the range of − 1.0 to 1.3 V \\u003cem\\u003evs\\u003c/em\\u003e SCE at a scan rate of 50 mV s\\u003csup\\u003e− 1\\u003c/sup\\u003e for 10 cycles. The obtained Ag\\u003csub\\u003e(a)\\u003c/sub\\u003e electrode was rinsed with deionized water and then dried. For comparison, the activated Cu mesh (Cu\\u003csub\\u003e(a)\\u003c/sub\\u003e) and Co plate (Co\\u003csub\\u003e(a)\\u003c/sub\\u003e) electrodes were synthesized by the same procedure.\\u003c/p\\u003e\\u003ch2\\u003eCharacterizations\\u003c/h2\\u003e\\u003cp\\u003eScanning electron microscopy (SEM) images were obtained from a German ZEISS Gemini SEM with an accelerating voltage of 20 kV. Transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM, Tecnai G2 F30) images were acquired at an operating voltage of 300 kV. X-ray diffraction (XRD) patterns were performed by the X’Pert PRO XRD diffractometer from PANalytical, Netherlands, with a Cu Kα radiation (λ = 0.1541 nm). X-ray photoelectron spectroscopy (XPS) measured were carried out on a Thermo Scientific K-Alpha X-ray photoelectron spectrometer using the Al Kα source at a chamber pressure of 2 × 10\\u003csup\\u003e−\\u003c/sup\\u003e⁷ mbar. The PHS-3C pH meter (Thunder Magnetic, Shanghai Yidian Scientific Instrument Co., Ltd.) was used to measure the solution pH.\\u003c/p\\u003e\\u003ch2\\u003eElectrochemical measurements\\u003c/h2\\u003e\\u003cp\\u003eThe electrochemical experiments were performed in a three-electrode H-cell (separated by Nafion 117 membrane) on the CHI 760E workstation (CH Instruments Inc., Shanghai) without any \\u003cem\\u003eiR\\u003c/em\\u003e-compensation, where Pt plate (1 × 2 cm\\u003csup\\u003e\\u003cspan citationid=\\\"CR2\\\" class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e), Ag\\u003csub\\u003e(a)\\u003c/sub\\u003e electrode (1 × 2 cm\\u003csup\\u003e\\u003cspan citationid=\\\"CR2\\\" class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e\\u003c/sup\\u003e), and Ag/AgCl (saturated KCl) electrode were used as a counter, working, and reference electrodes, respectively. Notably, all potentials for electrocatalysis in the three-electrode H-cell are reported with respect to the Ag/AgCl electrode in this paper. The cathode compartment was filled with 40 mL of different concentrations (0.01, 0.03, 0.3, and 0.5 M) of electrolytes (TBAT, TBAB, TMAH, LiOAc, LiOAc·2H\\u003csub\\u003e2\\u003c/sub\\u003eO, and LiClO\\u003csub\\u003e4\\u003c/sub\\u003e) in CH\\u003csub\\u003e3\\u003c/sub\\u003eOH solvent, with or without 10 mM TCMP. The anode compartment was filled with 1 M H\\u003csub\\u003e2\\u003c/sub\\u003eSO\\u003csub\\u003e4\\u003c/sub\\u003e. Before all the electrochemical measurements, the inert nitrogen (N\\u003csub\\u003e2\\u003c/sub\\u003e) was introduced into solution for 20 min to remove the undesired side reactions. Then different gases (N\\u003csub\\u003e2\\u003c/sub\\u003e, air, or O\\u003csub\\u003e2\\u003c/sub\\u003e) with the flow rate of 0.2 L min\\u003csup\\u003e− 1\\u003c/sup\\u003e were purged into the electrolyte during the whole test. Linear sweep voltammetry (LSV) tests were conducted in the three-electrodes system at a scan rate of 10 mV s\\u003csup\\u003e− 1\\u003c/sup\\u003e. \\u003cem\\u003eIn-situ\\u003c/em\\u003e electrochemical impedance spectroscopy (EIS) was employed on a ZAHNER Zennium electrochemical workstation over the frequency of 0.01 ~ 10\\u003csup\\u003e5\\u003c/sup\\u003e Hz at potential range from 0.2 to − 1.4 V \\u003cem\\u003evs\\u003c/em\\u003e Ag/AgCl (an interval of 0.2 V) with or without TCMP and O\\u003csub\\u003e2\\u003c/sub\\u003e. Chronopotentiometry was used for electrolysis under different conditions. The two-electrode flow electrolyzer consists of anode and cathode chambers, assembled with stainless steel bolts and sealed with washers. Carbon paper and Ag\\u003csub\\u003e(a)\\u003c/sub\\u003e electrodes (2 × 2 cm\\u003csup\\u003e− 2\\u003c/sup\\u003e) were used as a counter and working electrodes, respectively, using the Nafion 117 proton membrane for separation. During the test, high purity O\\u003csub\\u003e2\\u003c/sub\\u003e was fed into the cathode storage tank at a rate of 0.2 L·min\\u003csup\\u003e− 1\\u003c/sup\\u003e. The anolyte was 30 mL 1 M H\\u003csub\\u003e2\\u003c/sub\\u003eSO\\u003csub\\u003e4\\u003c/sub\\u003e, and the catholyte was 30 mL 20 mM TCMP with 30 mM TBAT in CH\\u003csub\\u003e3\\u003c/sub\\u003eOH. Two peristaltic pumps were used to transport the solution to the chambers.\\u003c/p\\u003e\\u003cp\\u003e \\u003cb\\u003eIn-situ\\u003c/b\\u003e \\u003cb\\u003eRaman spectra\\u003c/b\\u003e\\u003c/p\\u003e\\u003cp\\u003eElectrochemical \\u003cem\\u003ein-situ\\u003c/em\\u003e Raman spectra were detected on the high-speed and high-resolution confocal Raman spectrometer (LabRAM Odyssey, HORIBA France SAS) with the excitation wavelength of 532 nm. 0.3 M LiOAc·2H\\u003csub\\u003e2\\u003c/sub\\u003eO solution using CH\\u003csub\\u003e3\\u003c/sub\\u003eOH as solvent with or without TCMP (10 mM) in O\\u003csub\\u003e2\\u003c/sub\\u003e or N\\u003csub\\u003e2\\u003c/sub\\u003e saturated environment was used as the electrolyte. The applied potential was carried out from OCP to − 1.4 V \\u003cem\\u003evs\\u003c/em\\u003e Ag/AgCl with an interval of 0.1 V.\\u003c/p\\u003e\\u003cp\\u003e \\u003cb\\u003eIn-situ\\u003c/b\\u003e \\u003cb\\u003eFTIR spectra\\u003c/b\\u003e\\u003c/p\\u003e\\u003cp\\u003eElectrochemical \\u003cem\\u003ein-situ\\u003c/em\\u003e Fourier transform infrared spectra (FTIR) was measured by Bruker INVENIO-S (Bruker Optics GmbH\\u0026amp;Co. KG) using attenuated total reflection (ATR) mode. Concretely, 2 mg catalyst was dispersed into the mixture of ethanol (400 µL) and Nafion (100 µL) for sonication (30 min). The as-prepared catalyst ink (2 mg) was applied to the surface of the gold-plated silicon crystal, assembling as a working electrode. The measurements were conducted in a spectra-electrochemical cell containing 30 mM TBAT methanol solution with or without TCMP and O\\u003csub\\u003e2\\u003c/sub\\u003e. The spectra were collected at various potentials from OCP to − 1.4 V \\u003cem\\u003evs\\u003c/em\\u003e Ag/AgCl with an interval of 0.1 V.\\u003c/p\\u003e\\u003ch2\\u003eEPR experiment\\u003c/h2\\u003e\\u003cp\\u003eElectron paramagnetic resonance (EPR) spectra were recorded on a Bruker A300 spectrophotometer (Germany) using 20 mW microwave power and 100 kHz field modulation with the amplitude of 1 G. The g-values for each EPR spectrum were extracted from simulations performed using EasySpin (v5.2.23). The sample was prepared by the following process: 10 mg catalyst was dispersed in CH\\u003csub\\u003e3\\u003c/sub\\u003eOH (5 mL) under sonication. Before testing, 200 µL of the mixed solution was taken out, followed by the addition of 100 µL of capture agents. The time-dependent spectra were collected at the potentials of − 0.6 V \\u003cem\\u003evs\\u003c/em\\u003e Ag/AgCl.\\u003c/p\\u003e\\u003ch2\\u003eProducts analysis\\u003c/h2\\u003e\\u003cp\\u003eThe concentration of TCMP and its products in the reaction system were quantified using a Thermo Scientific Dionex Ultimate 3000 high-performance liquid chromatography (HPLC) system. The HPLC system was equipped with a chromatographic column (Ultimate AQ-C18, 250 mm × 4.6 mm, 5 µm) and a UV-visible detector (λ = 230 nm) to ensure effective separation of reactants and products. A sample volume of 10 µL was injected, and the column temperature was maintained at 35℃. The mobile phase for the HPLC consisted of 0.03 M H\\u003csub\\u003e3\\u003c/sub\\u003ePO₄, CH\\u003csub\\u003e3\\u003c/sub\\u003eOH, and acetonitrile, with a flow rate of 1 mL·min⁻¹ using a gradient elution method. The performance evaluation indicators include conversion (Con.), selectivity (Sel.), yield and Faradaic efficiency (FE) based on the following equation:\\u003c/p\\u003e\\u003cdiv id=\\\"Equ1\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ1\\\" name=\\\"EquationSource\\\"\\u003e\\n$$\\\\:\\\\text{C}\\\\text{o}\\\\text{n}.\\\\left(\\\\text{%}\\\\right)=\\\\frac{\\\\text{C}\\\\text{o}\\\\text{n}\\\\text{s}\\\\text{u}\\\\text{m}\\\\text{p}\\\\text{t}\\\\text{i}\\\\text{o}\\\\text{n}\\\\:\\\\text{o}\\\\text{f}\\\\:\\\\text{r}\\\\text{e}\\\\text{a}\\\\text{c}\\\\text{t}\\\\text{a}\\\\text{n}\\\\text{t}\\\\text{s}}{\\\\text{T}\\\\text{h}\\\\text{e}\\\\:\\\\text{t}\\\\text{o}\\\\text{t}\\\\text{a}\\\\text{l}\\\\:\\\\text{a}\\\\text{m}\\\\text{o}\\\\text{u}\\\\text{n}\\\\text{t}\\\\:\\\\text{o}\\\\text{f}\\\\:\\\\text{r}\\\\text{e}\\\\text{a}\\\\text{c}\\\\text{t}\\\\text{a}\\\\text{n}\\\\text{t}\\\\text{s}}\\\\times\\\\:100\\\\:\\\\text{%}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e1\\u003c/div\\u003e\\u003c/div\\u003e\\u003cdiv id=\\\"Equ2\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ2\\\" name=\\\"EquationSource\\\"\\u003e\\n$$\\\\:\\\\text{S}\\\\text{e}\\\\text{l}.\\\\:\\\\left(\\\\text{%}\\\\right)=\\\\frac{\\\\text{T}\\\\text{h}\\\\text{e}\\\\:\\\\text{a}\\\\text{m}\\\\text{o}\\\\text{u}\\\\text{n}\\\\text{t}\\\\:\\\\text{o}\\\\text{f}\\\\:\\\\text{t}\\\\text{a}\\\\text{r}\\\\text{g}\\\\text{e}\\\\text{t}\\\\:\\\\text{p}\\\\text{r}\\\\text{o}\\\\text{d}\\\\text{u}\\\\text{c}\\\\text{t}\\\\:}{\\\\text{C}\\\\text{o}\\\\text{n}\\\\text{s}\\\\text{u}\\\\text{m}\\\\text{p}\\\\text{t}\\\\text{i}\\\\text{o}\\\\text{n}\\\\:\\\\text{o}\\\\text{f}\\\\:\\\\text{r}\\\\text{e}\\\\text{a}\\\\text{c}\\\\text{t}\\\\text{a}\\\\text{n}\\\\text{t}\\\\text{s}}\\\\times\\\\:100\\\\:\\\\text{%}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e2\\u003c/div\\u003e\\u003c/div\\u003e\\u003cdiv id=\\\"Equ3\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ3\\\" name=\\\"EquationSource\\\"\\u003e\\n$$\\\\:\\\\text{Y}\\\\text{i}\\\\text{e}\\\\text{l}\\\\text{d}\\\\:\\\\left(\\\\text{%}\\\\right)=\\\\frac{\\\\text{T}\\\\text{h}\\\\text{e}\\\\:\\\\text{a}\\\\text{m}\\\\text{o}\\\\text{u}\\\\text{n}\\\\text{t}\\\\:\\\\text{o}\\\\text{f}\\\\:\\\\text{t}\\\\text{a}\\\\text{r}\\\\text{g}\\\\text{e}\\\\text{t}\\\\:\\\\text{p}\\\\text{r}\\\\text{o}\\\\text{d}\\\\text{u}\\\\text{c}\\\\text{t}\\\\:}{\\\\text{T}\\\\text{h}\\\\text{e}\\\\:\\\\text{t}\\\\text{o}\\\\text{t}\\\\text{a}\\\\text{l}\\\\:\\\\text{a}\\\\text{m}\\\\text{o}\\\\text{u}\\\\text{n}\\\\text{t}\\\\:\\\\text{o}\\\\text{f}\\\\:\\\\text{r}\\\\text{e}\\\\text{a}\\\\text{c}\\\\text{t}\\\\text{a}\\\\text{n}\\\\text{t}\\\\text{s}}\\\\times\\\\:100\\\\:\\\\text{%}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e3\\u003c/div\\u003e\\u003c/div\\u003e\\u003cdiv id=\\\"Equ4\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ4\\\" name=\\\"EquationSource\\\"\\u003e\\n$$\\\\:\\\\text{F}\\\\text{E}\\\\:\\\\left(\\\\text{%}\\\\right)=\\\\frac{n\\\\times\\\\:\\\\text{T}\\\\text{h}\\\\text{e}\\\\:\\\\text{a}\\\\text{m}\\\\text{o}\\\\text{u}\\\\text{n}\\\\text{t}\\\\:\\\\text{o}\\\\text{f}\\\\:\\\\text{t}\\\\text{a}\\\\text{r}\\\\text{g}\\\\text{e}\\\\text{t}\\\\:\\\\text{p}\\\\text{r}\\\\text{o}\\\\text{d}\\\\text{u}\\\\text{c}\\\\text{t}\\\\:\\\\left(\\\\text{m}\\\\text{o}\\\\text{l}\\\\right)\\\\times\\\\:F}{\\\\text{T}\\\\text{h}\\\\text{e}\\\\text{o}\\\\text{r}\\\\text{e}\\\\text{t}\\\\text{i}\\\\text{c}\\\\text{a}\\\\text{l}\\\\:\\\\text{c}\\\\text{o}\\\\text{n}\\\\text{s}\\\\text{u}\\\\text{m}\\\\text{p}\\\\text{t}\\\\text{i}\\\\text{o}\\\\text{n}\\\\:\\\\text{o}\\\\text{f}\\\\:\\\\text{t}\\\\text{o}\\\\text{t}\\\\text{a}\\\\text{l}\\\\:\\\\text{c}\\\\text{h}\\\\text{a}\\\\text{r}\\\\text{g}\\\\text{e}}\\\\times\\\\:100\\\\:\\\\text{%}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e4\\u003c/div\\u003e\\u003c/div\\u003e\\u003cp\\u003ewhere \\u003cem\\u003en\\u003c/em\\u003e represents the number of electrons transferred to form MCN, and \\u003cem\\u003eF\\u003c/em\\u003e is the Faraday constant (96,485 C·mol\\u003csup\\u003e− 1\\u003c/sup\\u003e).\\u003c/p\\u003e\\u003ch2\\u003efs-TAS\\u003c/h2\\u003e\\u003cp\\u003eFemtosecond transient absorption spectroscopy (fs-TAS) was performed on Ultrafast Systems Helios (USA), and the parameters used in the experiment are as follows: Pump energy: 962 µW; Pump wavelength: 350 nm; Cuvette length: 2 mm; Comments: time zero: 114.453 ps; Averaging time: 0.3 s; Number of scans: 2; Measurement time: 00:11:26; Time units: ps. The absorption spectra of transient products can be obtained by detecting the absorption of light, allowing for direct detection of transient products based on the absorption spectra.\\u003c/p\\u003e\\u003ch2\\u003eIsotope labeling experiments\\u003c/h2\\u003e\\u003cp\\u003e \\u003csup\\u003e \\u003cspan citationid=\\\"CR18\\\" class=\\\"CitationRef\\\"\\u003e18\\u003c/span\\u003e \\u003c/sup\\u003eO\\u003csub\\u003e2\\u003c/sub\\u003e (≥ 99%, Wuhan Isotope Technology Co., Ltd) was used as the oxygen source to label substrate. The isotope labeling experiments were carried out in an H-type electrolytic cell containing 1 M H\\u003csub\\u003e2\\u003c/sub\\u003eSO\\u003csub\\u003e4\\u003c/sub\\u003e anolyte and 30 mM LiOAc·2H\\u003csub\\u003e2\\u003c/sub\\u003eO (TBAT as solvent) catholyte with 10 mM TCMP. The electrolysis was taken out for 6 h at the potential of -0.6 V \\u003cem\\u003evs\\u003c/em\\u003e Ag/AgCl. Then, the sample was analyzed by LCMS. The H isotope tracing was also conducted using CD\\u003csub\\u003e3\\u003c/sub\\u003eOD (99.8%, MERYER) instead of CH\\u003csub\\u003e3\\u003c/sub\\u003eOH solvent.\\u003c/p\\u003e\\u003ch2\\u003eLCMS determination\\u003c/h2\\u003e\\u003cp\\u003eLCMS was performed on Agilent 1290uplc-QTOF6550 instrument. The specific parameters are as follows: Mobile phase A: 0.1% formic acid aqueous solution; Mobile phase B: methanol acetonitrile = 1:1 solution; The ratio of phase A to phase B is 70 : 30, The flow rate: 0.3 mL min\\u003csup\\u003e− 1\\u003c/sup\\u003e; The injection volume: 5 µL; Chromatographic column: Waters BEH C18 ( inner diameter: 2.1 mm; column length: 100 mm; and particle size: 1.7 µm); Mass spectrometry scanning range: primary 50–600 m/z; Sheath gas temp 350 ℃; Sheath gas flow 12 L min\\u003csup\\u003e− 1\\u003c/sup\\u003e; ESI mode: voltage 3200 V.\\u003c/p\\u003e\\u003ch2\\u003eDFT calculations\\u003c/h2\\u003e\\u003cp\\u003eAll calculations were performed with periodic DFT using the Gaussian plane wave method implemented in CP2K’s Quickstep module\\u003csup\\u003e\\u003cspan citationid=\\\"CR60\\\" class=\\\"CitationRef\\\"\\u003e60\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR61\\\" class=\\\"CitationRef\\\"\\u003e61\\u003c/span\\u003e\\u003c/sup\\u003e. The explorative studies of the catalysts structure were performed using the molecularly optimized basis set DZVP-MOLOPT-SR-GTH for each atom with a Goedecker-Teter-Hutter (GTH) pseudopotential\\u003csup\\u003e\\u003cspan citationid=\\\"CR62\\\" class=\\\"CitationRef\\\"\\u003e62\\u003c/span\\u003e\\u003c/sup\\u003e. The calculations were conducted using the generalized gradient approximation and the Perdew-Burke-Ernzerhof (PBE) functional\\u003csup\\u003e\\u003cspan citationid=\\\"CR63\\\" class=\\\"CitationRef\\\"\\u003e63\\u003c/span\\u003e\\u003c/sup\\u003e with DFT-D3 correction\\u003csup\\u003e\\u003cspan citationid=\\\"CR64\\\" class=\\\"CitationRef\\\"\\u003e64\\u003c/span\\u003e,\\u003cspan citationid=\\\"CR65\\\" class=\\\"CitationRef\\\"\\u003e65\\u003c/span\\u003e\\u003c/sup\\u003e. An energy convergence for the self-consistent field (SCF) calculation was set to 2 × 10\\u003csup\\u003e− 6\\u003c/sup\\u003e Hartree. An energy cutoff of 400 Ry was used throughout the calculations. The input file was generated by Multiwfn\\u003csup\\u003e\\u003cspan citationid=\\\"CR66\\\" class=\\\"CitationRef\\\"\\u003e66\\u003c/span\\u003e\\u003c/sup\\u003e. A 3 × 3 × 1 supercell with 3-layer atoms was employed for Ag (111) surfaces model according to the maximum crystal facet in XRD. The vacuum slab was 10 Å to minimize the interaction between slabs. In order to obtain more precise energy, the TZV2P-MOLOPT-PBE-GTH basis set with 3 × 3 × 1 \\u003cem\\u003ek\\u003c/em\\u003e-points was employed and the cutoff energy further increase to 400 eV when calculated single point energy.\\u003c/p\\u003e\\u003cp\\u003eThe Gibbs free energy for each reaction intermediate is defined as fellow equation:\\u003cspan class=\\\"InlineEquation\\\"\\u003e\\u003cspan class=\\\"mathinline\\\"\\u003e\\\\(\\\\:G={E}_{DFT}+{E}_{ZPE}-TS\\\\)\\u003c/span\\u003e\\u003c/span\\u003e\\u003c/p\\u003e\\u003cp\\u003eE\\u003csub\\u003eDFT\\u003c/sub\\u003e is the total energy of reaction intermediate model. E\\u003csub\\u003eZPE\\u003c/sub\\u003e is zero-point energy estimated within the harmonic approximation, and TS is the entropy at 298.15 K.\\u003c/p\\u003e\"},{\"header\":\"Declarations\",\"content\":\"\\u003ch2\\u003eAcknowledgements\\u003c/h2\\u003e \\u003cp\\u003eThe authors gratefully acknowledge the support from the National Nature Science Foundation of China (No. 22472150, 22302175), and the Natural Science Foundation of Zhejiang Province (No. LQ24E010010).\\u003c/p\\u003e\"},{\"header\":\"References\",\"content\":\"\\u003col\\u003e\\u003cli\\u003e\\u003cspan\\u003eNagendramma P, Kaul S (2012) Development of ecofriendly/biodegradable lubricants: An overview. Renew Sust Energy Rev 16:764\\u0026ndash;774\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eFerreira GF et al (2021) Mono- and diglyceride production from microalgae: Challenges and prospects of high-value emulsifiers. Trends Food Sci Technol 118:589\\u0026ndash;600\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eAzri NA et al (2022) Batch-to-continuous transition in the specialty chemicals industry: Impact of operational differences on the production of dispersants. Chem Eng J 445:136775\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eZhou X et al (2024) Entropy-assisted anion-reinforced solvation structure for fast-charging sodium-ion full batteries. Angew Chem Int Ed 63:e202410494\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eS\\u0026Aacute; AGA et al (2017) A review on enzymatic synthesis of aromatic esters used as flavor ingredients for food, cosmetics and pharmaceuticals industries. Trends Food Sci Technol 69:95e105\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eHuang D et al (2015) Isoniazid conjugated poly(lactide-co-glycolide): Long-term controlled drug release and tissue regeneration for bone tuberculosis therapy. Biomaterials 52:417e425\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eNimbkar S et al (2022) Medium chain triglycerides (MCT): State-of-the-art on chemistry, synthesis, health benefits and applications in food industry. Compr Rev Food Sci Food Saf 21:843\\u0026ndash;867\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eLiu Y et al (2022) Sustainable nano-pesticide platform based on pyrethrins II for prevention and control monochamus alternatus. J Nanobiotechnol 20:183\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003ePham PH et al (2023) Electricity-driven recycling of ester plastics using one-electron electro-organocatalysis. Chem Catal 3:100675\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eGlobal esters market \\u0026ndash; Industry trends and forecast to 2029. Data Bridge Market Research. \\u003cspan class=\\\"ExternalRef\\\"\\u003e\\u003cspan class=\\\"RefSource\\\"\\u003ehttps://www.databridgemarketresearch.com/zh/reports/global-esters-market\\u003c/span\\u003e\\u003cspan address=\\\"https://www.databridgemarketresearch.com/zh/reports/global-esters-market\\\" targettype=\\\"URL\\\" class=\\\"RefTarget\\\"\\u003e\\u003c/span\\u003e\\u003c/span\\u003e\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eBarletta M et al (2022) Poly(butylene succinate) (PBS): Materials, processing, and industrial applications. Prog Polym Sci 132:101579\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eZhang B et al (2024) Ambient-pressure alkoxycarbonylation for sustainable synthesis of ester. Nat Commun 15:7837\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eLong F et al (2021) State-of-the-art technologies for biofuel production from triglycerides: A review. Renew Sust Energy Rev 148:111269\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eCai Q et al (2021) Catalyst-free synthesis of polyesters via conventional melt polycondensation. Mater Today 51:155\\u0026ndash;164\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eHu Y et al (2021) Direct oxidative esterification of alcohols catalyzed by a nitrogen-doped carbon black-supported PdBi bimetallic catalyst under ambient conditions. J Mater Sci 56:7308\\u0026ndash;7320\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eWang L et al (2024) Enzymatic synthesis of pyridine heterocyclic compounds and their thermal stability. 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Nat Catal 3:649\\u0026ndash;655\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eChen J-Q et al (2021) Efficient access to aliphatic esters by photocatalyzed alkoxycarbonylation of alkenes with alkyloxalyl chlorides. Nat Commun 12:5328\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eChen H et al (2023) Highly efficient C@Ni-Pd bifunctional electrocatalyst for energy-saving hydrogen evolution and value-added chemicals co-production from ethanol aqueous solution. Chem Eng J 474:145639\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eMondal B et al (2021) Unraveling the mechanisms of electrocatalytic oxygenation and dehydrogenation of organic molecules to value-added chemicals over a Ni\\u0026ndash;Fe oxide catalyst. 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J Electrochem Soc 171\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eWu H et al (2024) Silver nanoparticles catalyzed electrochemical hydrodechlorination of dichloromethane to methane in N,N-dimethylformamide using water as hydrogen donor. Sep Purif Technol 331\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eWei D et al (2024) Coordination confined silver-organic framework for high performance electrochemical deionization. Adv Sci 11:2401174\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eFu X et al (2024) Ag\\u0026ndash;Ru interface for highly efficient hydrazine assisted water electrolysis. Energy Environ Sci 17:2279\\u0026ndash;2286\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eYuan Y et al (2024) Electrocatalytic ORR\\u0026ndash;coupled ammoximation for efficient oxime synthesis. Sci Adv 10:eado1755\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eMa L et al (2024) Promoting electrocatalytic glycerol CC bond cleavage to formate coupled with H\\u003csub\\u003e2\\u003c/sub\\u003e production over a Cu\\u003csub\\u003ex\\u003c/sub\\u003eNi\\u003csub\\u003e2\\u0026ndash;x\\u003c/sub\\u003eP catalyst. \\u003cem\\u003eAdv. Energy Mater.\\u003c/em\\u003e Adv. Energy Mater. 2401061, (2024)\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eLeow WR et al (2020) Chloride-mediated selective electrosynthesis of ethylene and propylene oxides at high current density. Science 368:1228\\u0026ndash;1233\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eDong J-C et al (2018) In situ Raman spectroscopic evidence for oxygen reduction reaction intermediates at platinum single-crystal surfaces. Nat Energy 4:60\\u0026ndash;67\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eDong J-C et al (2020) Direct in situ Raman spectroscopic evidence of oxygen reduction reaction intermediates at high-index pt(hkl) surfaces. J Am Chem Soc 142:715\\u0026ndash;719\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003ePeng Z et al (2015) Direct detection of the superoxide anion as a stable intermediate in the electroreduction of oxygen in a non-aqueous electrolyte containingphenol as a proton source. Angew Chem Int Ed 54:8165\\u0026ndash;8168\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eLei L et al (2024) From synthesis to mechanisms: In-depth exploration ofthe dual-atom catalytic mechanisms toward oxygen electrocatalysis. Adv Mater 36:2311434\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eTian Q et al (2024) Hydrogen peroxide electrosynthesis via selective oxygen reduction reactions through interfacial reaction microenvironment engineering. \\u003cem\\u003eAdv. Mater.\\u003c/em\\u003e, Adv. Mater. 2414490, (2024)\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eYang S et al (2024) The mechanism of water oxidation using transition metal-based heterogeneous electrocatalysts. Chem Soc Rev 53:5593\\u0026ndash;5625\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eCheon S et al (2024) Neighboring catalytic sites are essential for electrochemical dechlorination of 2\\u0026ndash;chlorophenol. J Am Chem Soc 146:25151\\u0026ndash;25157\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eDang K et al (2022) Boosting electrochemical styrene transformation via tandem water oxidation over a single-atom Cr\\u003csub\\u003e1\\u003c/sub\\u003e/CoSe\\u003csub\\u003e2\\u003c/sub\\u003e catalyst. Adv Mater 34:2200302\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eJiang J et al (2024) In situ activation of molecular oxygen at intermetallic spacing-optimized iron network-like sites for boosting electrocatalytic oxygen reduction. Small 20:2310163\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eNasima F, Nadeem MA (2023) Understanding the mechanism and synergistic interaction of cobalt-based electrocatalysts containing nitrogen-doped carbon for 4 e\\u003csup\\u003e-\\u003c/sup\\u003e ORR. 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Comput Phys Commun 167:103\\u0026ndash;128Quickstep\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eVandeVondele J, Hutter J (2007) Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases. J Chem Phys 127:114105\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003ePerdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77:3865\\u0026ndash;3868\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eGrimme S, Ehrlich S, Goerigk L (2011) Effect of the damping function in dispersion corrected density functional theory. J Comput Chem 32:1456\\u0026ndash;1465\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eGrimme S et al (2010) A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys 132:154104\\u003c/span\\u003e\\u003c/li\\u003e \\u003cli\\u003e\\u003cspan\\u003eLu T, Chen F, Multiwfn (2012) A multifunctional wavefunction analyzer. J Comput Chem 33:580\\u0026ndash;592\\u003c/span\\u003e\\u003c/li\\u003e\\u003c/ol\\u003e\"}],\"fulltextSource\":\"\",\"fullText\":\"\",\"funders\":[],\"hasAdminPriorityOnWorkflow\":false,\"hasManuscriptDocX\":true,\"hasOptedInToPreprint\":true,\"hasPassedJournalQc\":\"\",\"hasAnyPriority\":true,\"hideJournal\":false,\"highlight\":\"\",\"institution\":\"\",\"isAcceptedByJournal\":true,\"isAuthorSuppliedPdf\":false,\"isDeskRejected\":\"\",\"isHiddenFromSearch\":false,\"isInQc\":false,\"isInWorkflow\":false,\"isPdf\":false,\"isPdfUpToDate\":true,\"isWithdrawnOrRetracted\":false,\"journal\":{\"display\":true,\"email\":\"info@researchsquare.com\",\"identity\":\"researchsquare\",\"isNatureJournal\":false,\"hasQc\":true,\"allowDirectSubmit\":true,\"externalIdentity\":\"\",\"sideBox\":\"\",\"snPcode\":\"\",\"submissionUrl\":\"/submission\",\"title\":\"Research Square\",\"twitterHandle\":\"researchsquare\",\"acdcEnabled\":true,\"dfaEnabled\":false,\"editorialSystem\":\"\",\"reportingPortfolio\":\"\",\"inReviewEnabled\":false,\"inReviewRevisionsEnabled\":true},\"keywords\":\"Electrocatalytic Esters Synthesis, Oxygen Reduction Reaction, Dechlorination, Cascade reaction, Acyl chloride\",\"lastPublishedDoi\":\"10.21203/rs.3.rs-5948207/v1\",\"lastPublishedDoiUrl\":\"https://doi.org/10.21203/rs.3.rs-5948207/v1\",\"license\":{\"name\":\"CC BY 4.0\",\"url\":\"https://creativecommons.org/licenses/by/4.0/\"},\"manuscriptAbstract\":\"\\u003cp\\u003eEster compounds as one of the most important organic chemicals are extensively used in chemical industry, medicines, food, plastics, cosmetics and other applications. Traditional ester synthesis is impeded by challenges of slow reaction kinetics, harsh conditions, and environmental concerns. Here, we propose a green and efficient route for synthesis of esters via an electrochemical dechlorination-oxygen insertion cascaded with chemical nucleophilic reaction. A high selectivity of 93.2%, and a yield of 92.5% for methyl 6-chloronicotinate (MCN) generation are obtained by electrochemical reduction of 2-chloro-5-trichloromethyl pyridine over the activated Ag electrode in an O\\u003csub\\u003e2\\u003c/sub\\u003e-saturated alcoholic solution. Electrochemical \\u003cem\\u003ein-situ\\u003c/em\\u003e characterizations, femtosecond transient absorption spectra, isotope labeling, and theoretical calculations elucidate that the formation of intermediate acyl chloride is a key step, which involves reactive oxygen species of oxygen reduction reaction (ORR) coupling with dechlorination intermediate. The involvement of O₂ alters the electrochemical reaction pathway from conventional hydrodechlorination to oxygenation-dechlorination process, which is attributed to the preferentially occurred ORR than hydrogen evolution reaction. The generated acyl chloride further facilitates the subsequent chemical reaction in an alcoholic solution for MCN synthesis. The broad substrate scope and excellent performance in a flow electrolyzer validate the scalability and potential of this electrocatalysis-cascaded chemistry system for sustainable industrial production.\\u003c/p\\u003e\",\"manuscriptTitle\":\"O2-Triggered Electrochemical Generation of Acyl Chloride Promoting Cascade Reaction of Esters Synthesis\",\"msid\":\"\",\"msnumber\":\"\",\"nonDraftVersions\":[{\"code\":1,\"date\":\"2025-03-27 10:12:12\",\"doi\":\"10.21203/rs.3.rs-5948207/v1\",\"editorialEvents\":[{\"type\":\"communityComments\",\"content\":0}],\"status\":\"published\",\"journal\":{\"display\":true,\"email\":\"info@researchsquare.com\",\"identity\":\"researchsquare\",\"isNatureJournal\":false,\"hasQc\":true,\"allowDirectSubmit\":true,\"externalIdentity\":\"\",\"sideBox\":\"\",\"snPcode\":\"\",\"submissionUrl\":\"/submission\",\"title\":\"Research Square\",\"twitterHandle\":\"researchsquare\",\"acdcEnabled\":true,\"dfaEnabled\":false,\"editorialSystem\":\"\",\"reportingPortfolio\":\"\",\"inReviewEnabled\":false,\"inReviewRevisionsEnabled\":true}}],\"origin\":\"\",\"ownerIdentity\":\"26fb6426-26c6-4ab0-8346-efe4115b3b48\",\"owner\":[],\"postedDate\":\"March 27th, 2025\",\"published\":true,\"recentEditorialEvents\":[],\"rejectedJournal\":[],\"revision\":\"\",\"amendment\":\"\",\"status\":\"published-in-journal\",\"subjectAreas\":[{\"id\":46253036,\"name\":\"Physical sciences/Chemistry/Electrochemistry/Electrocatalysis\"},{\"id\":46253037,\"name\":\"Physical sciences/Chemistry/Green chemistry\"}],\"tags\":[],\"updatedAt\":\"2025-08-08T21:47:08+00:00\",\"versionOfRecord\":{\"articleIdentity\":\"rs-5948207\",\"link\":\"https://doi.org/10.1021/jacs.5c07666\",\"journal\":{\"identity\":\"journal-of-the-american-chemical-society\",\"isVorOnly\":true,\"title\":\"Journal of the American Chemical Society\"},\"publishedOn\":\"2025-08-01 00:00:00\",\"publishedOnDateReadable\":\"August 1st, 2025\"},\"versionCreatedAt\":\"2025-03-27 10:12:12\",\"video\":\"\",\"vorDoi\":\"10.1021/jacs.5c07666\",\"vorDoiUrl\":\"https://doi.org/10.1021/jacs.5c07666\",\"workflowStages\":[]},\"version\":\"v1\",\"identity\":\"rs-5948207\",\"journalConfig\":\"researchsquare\"},\"__N_SSP\":true},\"page\":\"/article/[identity]/[[...version]]\",\"query\":{\"redirect\":\"/article/rs-5948207\",\"identity\":\"rs-5948207\",\"version\":[\"v1\"]},\"buildId\":\"XKTyCvWXoU3ODBz1xrDgd\",\"isFallback\":false,\"isExperimentalCompile\":false,\"dynamicIds\":[84888],\"gssp\":true,\"scriptLoader\":[]}","source_license":"CC-BY-4.0","license_restricted":false}