Regulation of Remote Sites to Enhance Pt Activity in the Hydrogenation of Sulfur-Containing Nitroarenes

Regulation of Remote Sites to Enhance Pt Activity in the Hydrogenation of Sulfur-Containing Nitroarenes | 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 Regulation of Remote Sites to Enhance Pt Activity in the Hydrogenation of Sulfur-Containing Nitroarenes Qihua Yang, Zhenchao Zhao, Haitao Chen, Zongpeng Ling, Jie Yu, and 5 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5861758/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Outer-sphere catalysis, commonly associated with enzyme catalysis and homogeneous catalysis, utilizes remote sites to drive reactions and is particularly effective for reactants that are toxic to the catalyst. However, this approach has been rarely explored in heterogeneous catalysis. In this study, we demonstrate the use of remote sites to enhance the activity of Pt nanoparticles (NPs) in the hydrogenation of sulfur-containing nitroarenes. Catalysts with Pt and MoO 3 co-deposited on TiO 2 efficiently catalyze the hydrogenation of 5-nitrobenzothiazole (NBZ) under mild conditions, achieving a conversion rate of 5448 mol NBZ · mol Pt ⁻¹ · h⁻¹, the highest reported to date, even with ppm levels of Pt. The optimized Pt density (~ 3 NPs per 1×10 4 nm 2 ) on the catalyst was found to favor HxMoO 3 mediated sequential H transfer from Pt to Mo and subsequently to the substrate. Higher Pt density may enhance H transfer to Mo, but the hydrogenation process becomes limited by the availability of HxMoO 3 for further H transfer to the substrate, revealing the intrinsic reason for the high activity of catalysts with ppm Pt. A direct H transfer pathway via HxMoO 3 to the substrate, rather than solvent-mediated proton-coupled electron transfer, was observed and confirmed through solvent isotope kinetic effects and solvent studies. Tuning remote sites on solid catalysts offers a promising strategy for developing catalysts with the minim use of precious metals in the hydrogenation of strongly coordinating reactants. Physical sciences/Chemistry/Catalysis/Heterogeneous catalysis Physical sciences/Chemistry/Green chemistry/Sustainability Remote site sulfur-containing compounds hydrogenation hydrogen spillover strong metal support interaction Figures Figure 1 Figure 2 Figure 3 Figure 4 Introduction The outer-sphere catalysis involves remote interactions between catalysts and reactants, commonly observed in homogeneous catalysis, enzyme catalysis, and electrosynthesis. 1 – 3 In this mechanism, the metal center does not directly coordinate with the substrate but facilitates the reaction by altering the environment around the substrate molecule or providing a suitable reaction site. For instance, in outer-sphere hydrogenation catalysis, the substrate does not bind to the metal, and the catalyst transfers a hydride and a proton to the unbound substrate either through a concerted or stepwise pathway. 1 Outer-sphere pathways are, in principle, accessible to non-precious metals and even nonmetal catalysts, and they can also be applied to poison-resistant catalytic systems. 4 This reaction mechanism is typically found in enzyme catalysis and homogeneous catalysis, but has been rarely reported for heterogeneous catalysis. 5 , 6 The hydrogenation of sulfur-containing nitroarenes to their corresponding sulfur-containing anilines is of significant importance for practical applications, as these anilines serve as crucial intermediates in various pharmaceuticals. 7 – 9 Developing robust catalysts with high resistance to sulfur poisoning is highly desirable for both fundamental research and practical applications. In heterogeneous catalysis, the hydrogenation of sulfur-containing compounds poses a significant challenge due to the strong coordination of sulfur atoms with metal sites, which greatly inhibits the activity of supported metal catalysts. 7 , 10 , 11 Several strategies have been proposed to enhance the sulfur resistance of supported metal catalysts for the hydrogenation of sulfur-containing compounds. 12 Transition metal sulfides, such as NiMoS and CoMoS as industrial hydrodesulfurization catalysts, are intrinsically resistant to sulfur poisoning, but viable to desulfurization at high temperature due to its low hydrogenation activity. 13 , 14 Recently, Glorius et al. discovered that noble metal sulfides, such as Ru-S catalysts with oxidized sulfur species, exhibit excellent performance in the hydrogenation of sulfur-containing quinolines to tetrahydroquinolines (THQs) under mild conditions. 15 Noble metals like Pd and Ru, when decorated with electron-rich atoms such as sulfur (S), phosphorus (P), or their related organic ligands, can effectively mitigate the poisoning effect of sulfur-containing substrates. 7 , 11 , 16 These strategies primarily focus on modulating the surface structure of metal sites, and high metal loading is still required for the catalytic conversion of sulfur-containing compounds. Recently, Pt/TiO 2 and Pt/MoO 3 catalysts were employed in the hydrogenation of 5-nitrobenzothiazole. 17 , 18 The results indicate that the oxygen vacancy (Ov) in Pt/TiO 2 and HxMoO 3 of Pt/MoO 3 serve as the actual hydrogenation sites. Similarly, Shimizu and colleagues found that the reduced Mo species were attributed to the active sites for hydrodeoxygenation in Pt-MoO 3 -catalyzed hydrodeoxygenation of sulfoxides to sulfides. 19 , 20 These examples highlight the in-situ generation of outer-sphere sites during hydrogenation and the critical role of hydrogen spillover. The in-situ formation of outer-sphere sites is closely associated with the strong metal-support interaction (SMSI) effect. 21 Generally, stronger SMSI promotes the formation of higher amounts of Ov or reduced Mo species but also leads to severe surface coverage of Pt, which restricts H 2 dissociation and hydrogen spillover. This contradiction limits the catalytic activity, necessitating high precious metal loading to achieve high conversion. 17 , 19 , 22 Therefore, the rational modulation of in-situ generated remote sites and hydrogen spillover is highly desirable to enhance the activity of supported metal catalysts and reduce the required amounts of precious metals in the hydrogenation of sulfur-containing compounds. Herein, the in-situ generated remote sites (reduced Mo species) were precisely modulated using Pt/Mo-TiO 2 as a model catalyst by controlling of the Pt-Mo/MoO 3 -TiO 2 interface (Scheme 1 ). The catalyst with 0.05 wt% Pt loading achieves the highest amounts of in-situ reduced Mo species and efficiently catalyzes the hydrogenation of 5-nitrobenzothiazole with a conversion rate of 5448 mol NBZ ·mol Pt ⁻¹·h⁻¹, superior to previously reported catalysts. This is attributed to the optimized Pt density, which balances the stepwise H transfer from Pt to Mo and then to 5-nitrobenzothiazole. Detailed mechanism studies demonstrate the interfacial confined H transfer plays a crucial role in the enhanced catalytic performance. Results and discussion Catalyst preparation and screening Mo-MO 2 (MO 2 = CeO 2 , SiO 2 , and ZrO 2 ) supports were prepared by loading (NH 4 ) 6 Mo 7 O 24 .4H 2 O on MO 2 , followed by calcination in an air atmosphere at 550 °C. Pt was loaded onto MO 2 -TiO 2 , MoO 3 , and TiO 2 using the wet impregnation method with H 2 reduction. The BET surface areas of Pt/Mo-TiO 2 catalysts are similar (ca. 24–25 m 2 /g), slightly lower than that of Pt/TiO 2 (33 m 2 /g) but significantly higher than Pt/MoO 3 (2 m 2 /g, Table S1 ). The Mo and Pt contents were determined to range from 0 to 20 wt% and 0.05 to 1 wt%, respectively. The BET surface area of control catalysts, 0.1Pt/5Mo-CeO 2 , 0.1Pt/5Mo-ZrO 2 and 0.1Pt/5Mo-SiO 2 with 0.1 wt% Pt and 5 wt% MoO 3 loading is in the range of 14–209 m 2 /g (Table S2). In the hydrogenation of 5-nitrobenzothiazole (NBZ), 0.1Pt/5Mo-CeO 2 and 0.1Pt/5Mo-ZrO 2 are almost inactive, while 0.1Pt/5Mo-SiO 2 showed 13% conversion (Table S2). To our delight, almost full conversion with > 99% selectivity to aminobenzothiazole (ABZ) was achieved over 0.1Pt/5Mo-TiO 2 under the similar conditions. These results demonstrate that 0.1Pt/5Mo-TiO 2 is an efficient catalyst for the hydrogenation of NBZ. Inspired by the high activity of 0.1Pt/5Mo-TiO 2 , the Mo and Pt loadings were further optimized. The reaction profiles (Fig. 1 A) reveal that all Pt/Mo-TiO 2 catalysts exhibit higher activity than Pt/TiO 2 . Over similar time intervals, the conversion increases as the Mo content in the catalysts rises, peaking at 15 wt% Mo, which achieves complete NBZ conversion within just 30 minutes. However, the conversion declines as the Mo loading further increases to 20 wt%, with a more pronounced decrease observed when pure MoO 3 is used as the support. As the Mo loading increases, the conversion rate (Fig. 1 B) gradually rises, reaching a maximum of 5448 mol NBZ ·mol Pt −1 ·h − 1 at 15 wt% Mo, before decreasing with further increase of Mo loading. Compared to Pt/Mo-TiO 2 catalysts, Pt/MoO 3 and Pt/TiO 2 exhibit relatively lower activity. The activity sequence follows the order: 0.05Pt/MoO 3 < 0.05Pt/TiO 2 < 0.05Pt/5Mo-TiO 2 < 0.05Pt/10Mo-TiO 2 < 0.05Pt/20Mo-TiO 2 < 0.05Pt/15Mo-TiO 2 . These results clearly demonstrate that the presence of MoO 3 significantly enhances the performance of Pt/TiO 2 , with the optimal Mo loading being 15 wt%. Furthermore, the catalytic performance of Pt/Mo-TiO 2 catalysts is strongly influenced by the amount of Pt present on the catalysts. The activity of Pt/15Mo-TiO 2 decreases sharply as the Pt loading increases. The reaction rate of 0.05Pt/15Mo-TiO 2 is approximately 20 times that of 1Pt/15Mo-TiO 2 . Compared to previously reported catalysts (Scheme 1 ), the precious metal loading of 0.05Pt/15Mo-TiO 2 is the lowest required to achieve high conversion in the hydrogenation of sulfur-containing compounds. Catalyst characterization To identify the key factors affecting the catalytic performance, the supported Pt catalysts were fully characterized. The XRD and Raman characterization results (Figure S1 A-B) reveal that only characteristic peaks assigned to rutile TiO 2 could be observed for all Pt/Mo-TiO 2 catalysts, demonstrating that Mo species are likely highly dispersed as a monolayer or in a few layers on the TiO 2 support. The signals of TiO 2 at 239, 447 and 610 cm − 1 decrease significantly after Mo loading in the Raman spectra of Pt/Mo-TiO 2 , implying the surface coverage of TiO 2 by Mo species (Figure S1 B). 23 , 24 For 0.05Pt/MoO 3 , distinct MoO 3 signals are clearly visible. Transmission electron microscopy (TEM) and high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) images show the existence of Pt nanoparticles ranging from 1.1 to 3.6 nm in size on the catalysts (Fig. 1 A and S2). From 0.05 Pt/TiO 2 to 0.05Pt/5Mo-TiO 2 and then to 0.05Pt/15Mo-TiO 2 , the Pt size gradually decreases from 2.1 to 1.5 and then to 1.1 nm, indicating that MoO 3 promotes Pt dispersion. 1Pt/15Mo-TiO 2 exhibits a relatively larger Pt size of 3.6 nm. Corresponding energy dispersive spectroscopy (EDS) elemental mapping images show the uniform distribution of Mo on TiO 2 and the preferential location of Pt on MoO 3 , suggesting close contact between Pt and Mo (Fig. 1 C-F). Only reduced Mo species including Mo 5+ (232.0 eV), Mo 4+ (231.0 eV), and Mo 3+ (229.5 eV) 24 are observed in the Mo 3d X-ray photoelectron spectroscopy (XPS) spectra of Pt/Mo-TiO 2 (Fig. 3 A), with Mo 5+ and Mo 4+ being dominant. The relative ratio of Mo 3+ increases as the Mo loading rises from 5 to 20 wt% for 0.05Pt/Mo-TiO 2 (Table S3). This indicates the complete reduction of MoO 3 during the catalyst preparation process and a deeper Mo reduction degree at higher MoO 3 loading, which may be associated with the stronger interaction between TiO 2 and MoO 3 at lower MoO 3 loading. With Pt loading increasing to 1 wt%, a slight increase in the ratios of Mo 4+ and Mo 3+ was observed for 1Pt/15Mo-TiO 2 compared to 0.05Pt/15Mo-TiO 2 . In addition to Mo 5+ and Mo 4+ , the presence of Mo 6+ (232.0 eV) with a relative ratio of 34% was clearly observed in the Mo 3d XPS spectrum of 0.05Pt/MoO 3 . No Mo 3+ were detected for 0.05Pt/MoO 3 , indicating that the formation of reduced Mo species can be efficiently modulated by loading MoO 3 on TiO 2 . 24 O1s XPS spectra (Figure S3A and Table S4) of Pt/Mo-TiO 2 show signals of bulk O of TiO 2 at 530.4 eV and hydroxyl O at 531.6 eV, arising from the reduction of MoO 3 due to hydrogen spillover. 19 The relative amount of hydroxyl increases as the Mo content and reaches a maximum at 15 wt% Mo loading, while no apparent changes were observed for 1Pt/15Mo-TiO 2 with increased Pt loading (Table S4). Substantial hydroxyl O species can also be observed for Pt/MoO 3 probably due to the formation of bulk HxMoO 3 near the surface. The binding energies of Pt 4f 7/2 gradually increase from 70.8 to 71.5 eV as Mo loading increases from 0 wt% to 100 wt% for 0.05Pt/Mo-TiO 2 . Similar increase in binding energy of Pt 4f 7/2 to 71.3 eV was also observed for 1Pt/15Mo-TiO 2 (Table S4), suggesting the electron transfer from Pt to Mo. The FT-IR spectra of CO adsorption on 0.05 wt% Pt loaded on Mo-TiO 2 , TiO 2 and MoO 3 were collected to explore the effect of Mo on the status of Pt (Fig. 3 B). A strong broad absorption band at 2071 cm − 1 assigned to CO adsorbed at the edge/corner of Pt NPs, along with weak signal of CO on Pt δ+ at 2100 cm − 1 and bridge-adsorbed CO near 1850 cm − 1 , were observed for 0.05Pt/TiO 2 . 25–27 All 0.05Pt/Mo-TiO 2 catalysts also display major CO adsorbed at the edge/corner of Pt NPs, but the bridge-adsorbed CO disappeared. The edge/corner adsorbed CO band blue-shifted accompanied with the reduction in band intensity for 0.05Pt/Mo-TiO 2 as the MoO 3 loading increased, which may be attributed to a pronounced SMSI effect. 28 1Pt/15Mo-TiO 2 (Figure S4) also shows edge/corner adsorbed CO with substantial reduction in peak intensity. No CO absorption band could be observed in the FT-IR spectrum of 0.05Pt/MoO 3 , indicating the sever surface coverage of Pt due to the SMSI. 29 In the H 2 -TPR profiles (Fig. 3 C and Figure S5), the reduction peaks below 200°C can be assigned to hydrogen intercalation into MoO 3 matrixes to form HxMoO 3 , and weak H 2 consumption peaks between 200 to 300 ºC are attributed to the formation of molybdenum suboxides (e.g., Mo 4 O 11 or MoO 3 − x ). 19,29 15Mo-TiO 2 shows a MoO 3 reduction peak near 390°C (Figure S5), much lower than MoO 3 (above 500 ºC), 24 , 29 indicating that TiO 2 promotes MoO 3 reduction. The lower temperature of the reduction peaks of Pt/MoTiO 2 and Pt/MoO 3 than those of MoO 3 and MoTiO 2 suggests that Pt facilitates Mo reduction. Pt/MoTiO 2 with Mo loading below 15 wt% mainly exhibits reduction peaks below 200°C, and that with ≥ 15 wt% Mo shows both low- and high-temperature peaks, indicating that HxMoO 3 species and molybdenum suboxides coexist in Pt/Mo-TiO 2 with Mo loading ≥ 15 wt%, while 0.05Pt/5Mo-TiO 2 and 0.05Pt/10Mo-TiO 2 contain only HxMoO 3 . Compared to 0.05Pt/MoO 3 , 0.05Pt/MoTiO 2 shows a lower-temperature reduction peak, possibly due to the high dispersion of MoO 3 on TiO 2 . 23 The reduction peak of 1Pt/15MoTiO 2 assigned to the formation of HxMoO 3 further moves down to 32°C, much lower than that of 0.05Pt/15MoTiO 2 , implying much easier hydrogen intercalation into MoO 3 at higher Pt loading (Figure S5). The H 2 consumption amounts assigned to the formation of HxMoO 3 increases from 0.05Pt/5Mo-TiO 2 to 0.05Pt/15Mo-TiO 2 , and then decreases for 0.05Pt/20Mo-TiO 2 (Table S5). It is interesting to mention that 0.05Pt/15Mo-TiO 2 and 1Pt/15Mo-TiO 2 have similar intercalated H contents (3.4 versus 3.7 mmol/g), verifying that ppm Pt is enough for the formation of substantial amounts of HxMoO 3 . Active sites identification Previous results suggest that HxMoO 3 of Pt/MoO 3 mainly serve as active sites for the hydrogenation of sulfur-containing compounds. 19 , 29 To identify the active sites involved in our catalysts, H 2 activated 0.05Pt/15Mo-TiO 2 and 0.05Pt/MoO 3 were used for NBZ hydrogenation under N 2 atmosphere (Figure S6). As expected, the product ABZ was detected for both samples, showing that HxMoO 3 acts as remote active sites for NBZ hydrogenation. Combined with H 2 consumption amounts from H 2 -TPR, about 50% and 10% stored H in HxMoO 3 of 0.05Pt/15Mo-TiO 2 and 0.05Pt/MoO 3 could be transferred to NBZ, respectively. The conversion rate per Pt atom of 0.05Pt/15Mo-TiO 2 is approximately 1.6 folds that of 0.05Pt/MoO 3 though the later has more than 5 folds HxMoO 3 than the former according to H 2 -TPR. This implies that the H species of HxMoO 3 in 0.05Pt/15Mo-TiO 2 is more efficiently transferred to NBZ than those in 0.05Pt/MoO 3 , possibly due to the high dispersion of MoO 3 on TiO 2 . Considering that HxMoO 3 is the active sites for NBZ hydrogenation, the activity of 0.05Pt/Mo-TiO 2 was related with amounts of intercalated H obtained from H 2 -TPR. A linear correlation was observed, further confirming that in situ formed surface HxMoO 3 is the main active site for NBZ hydrogenation (Fig. 4 A). The substantial deviation of 0.05Pt/MoO 3 likely arises from a combination of surface coverage by Pt nanoparticles due to strong SMSI and the limited exposure of bulk HxMoO 3 . 0.05Pt/15Mo-TiO 2 and 1Pt/15Mo-TiO 2 with similar amounts of intercalated H exhibit different activities at identical NBZ/Pt ratio or at similar catalyst weight (Figure S7). Because the two catalysts have different Pt size, Pt(C)/15Mo-TiO 2 catalysts were prepared by loading different amounts of ~ 2 nm Pt colloids on 15Mo-TiO 2 to exclude the influence of Pt size and investigate the role of Pt. The TEM images show that Pt(C)/15Mo-TiO 2 with Pt loading in the range of 0.05 wt% to 2 wt% have similar Pt size of about 2.0 nm (Figure S8). When tested for NBZ hydrogenation under the same catalyst mass, the per-Pt-atom activity of Pt(C)/15Mo-TiO 2 decreased from 1884 to 274 mol NBZ ·mol Pt ⁻¹·h⁻¹ as Pt loading increased, mirroring the trend in 0.05Pt/xMo-TiO 2 . In this case, varying the Pt content only changed the density of Pt NPs on the catalysts, thus, the number of Pt NPs per 1 x 10 4 nm² was calculated and corelated with the activity of Pt(C)/15Mo-TiO 2 (Fig. 4 A). 0.05Pt/15Mo-TiO 2 with low Pt density (three Pt nanoparticles per 1 x 10 4 nm²) achieved the highest activity. This suggests that low Pt density favored HxMoO 3 mediated sequential H transfer from Pt to Mo and subsequently to the substrate. Higher Pt density may enhance H transfer to Mo, but the hydrogenation process becomes limited by the availability of HxMoO 3 for further H transfer to the substrate, revealing the intrinsic reason for the high activity of 0.05Pt/15Mo-TiO 2 with ppm Pt. Reaction mechanism investigation Direct hydrogen transfer from Pt to NBZ is hindered by NBZ’s strong adsorption on the Pt surface. This was confirmed by testing the activity of 0.05Pt/TiO 2 and 0.05Pt/15Mo–TiO 2 in nitrobenzene (NB) hydrogenation to aniline (AN) in the presence and absence of the sulfur poison benzothiazole (Fig. 4 B). Although 0.05Pt/TiO 2 initially achieves a high reaction rate of 26522 mol AN ·mol Pt ⁻¹·h⁻¹, it drops to 291 mol AN ·mol Pt ⁻¹·h⁻¹ (nearly 99% loss) with benzothiazole, indicating that the sulfur-induced Pt site blockage impedes direct H transfer. In contrast, 0.05Pt/15Mo-TiO 2 retains 60% of its activity (falling from 15913 to 9753 mol AN ·mol Pt ⁻¹·h⁻¹), attributed to the existence of large amounts of remote sites. These findings confirm the H transfer from Pt to Mo and subsequently to NBZ. Kinetic studies with 0.05Pt/TiO 2 , 0.05Pt/15Mo-TiO 2 , and 1.0Pt/15Mo-TiO 2 (Figs. 5C-D) reveal similar hydrogen reaction orders (0.54–0.68). However, 0.05Pt/TiO 2 shows a more negative NBZ reaction order (-0.75) than the Pt/Mo-TiO 2 catalysts (in the range of -0.36 to -0.45), implying stronger NBZ adsorption on Pt/TiO 2 . The r H2 /r D2 ratio is 1.4–1.6 for all catalysts (Fig. 5E), but a distinct kinetic isotope effect (KIE) appears with the solvent. The r EtOH /r EtOD ratios are 2.4, 1.0, and 0.7 for 0.05Pt/TiO 2 , 0.05Pt/15Mo-TiO 2 , and 1Pt/15Mo-TiO 2 , respectively, indicating different H transfer route for the catalysts. The strong solvent KIE with Pt/TiO 2 suggests that protons of solvent are actively participating in the reaction, potentially involving hydrogen spillover through proton-coupled electron transfer during the hydrogenation process, which is further confirmed by the higher activity of 0.05Pt/TiO 2 in ethanol than in toluene in NBZ hydrogenation (Fig. 5e). For Pt/15Mo-TiO₂, the transfer of H from Pt to 15Mo-TiO 2 , and subsequently to substrate may occur directly through HxMoO 3 matrix. The similar activity of 0.05Pt/15Mo-TiO 2 in ethanol and toluene further confirms the direct H transfer via HxMoO 3 . 0.05Pt/15Mo-TiO 2 also demonstrated excellent activity and selectivity across a broad range of nitroarenes (Table 1 ), achieving up to >94% conversion with >98% selectivity to nitro hydrogenated products while tolerating chlorides, olefins, and other functionalized aromatics. It also exhibited strong sulfur resistance, efficiently hydrogenating mercaptans and thioethers within 1 hour at S/C ratios above 2000. In a continuous flow reactor (Figure S9), Pt/Mo-TiO 2 catalyst maintained a stable conversion rate at 118 mol NBZ ·mol Pt ⁻¹·h⁻¹ over 25 h, with a slight decrease to 97 mol NBZ ·mol Pt ⁻¹·h⁻¹ after 75 hours. In comparison, the 0.05Pt/MoO 3 catalyst exhibited a sharp decrease in conversion rate, dropping from 45 to 18 mol NBZ ·mol Pt ⁻¹·h⁻¹ within 75 hours. Discussion In the hydrogenation of sulfur containing compounds, the catalysts are often required to have high content of precious metal to achieve desirable conversion, due to the poisoning effect of sulfur atom. In this work, it was found that 0.05Pt/15Mo-TiO 2 with minim Pt content shows high activity in the hydrogenation of NBZ. The efficient conversion of NBZ over H 2 treated 0.05Pt/15Mo-TiO 2 in N 2 shows that HxMoO 3 is active site for NBZ hydrogenation, demonstrating the importance in the regulation of remote sites. The almost linear relationship of activity and HxMoO 3 of 0.05Pt/Mo-TiO 2 suggests that higher amounts of HxMoO 3 are favorable for the high activity. However, a contradiction was observed for 0.05Pt/15Mo-TiO 2 and 1Pt/15Mo-TiO 2 , showing that the amounts of HxMoO 3 are not the only factor influencing the activity. Pt(C)/15Mo-TiO 2 with similar Pt size but different Pt content was employed to investigate the role of Pt content in the hydrogenation of NBZ. It was found that the reaction rate decreases with the Pt content increasing. The optimized Pt density is three Pt NPs/1x 10 4 nm 2 , showing the important role of Pt/surface Mo ratio. In the hydrogenation of NBZ, the H 2 is dissociated on Pt NPs, the dissociated H intercalated into MoO 3 to form HxMoO 3 , then the product was formed by transferring H from HxMoO 3 to NBZ. When the H transfer rate from HxMoO 3 to NBZ is slower than the formation rate of HxMoO 3 , the H transfer from Pt to MoO 3 should be inhibited, as a result, lower Pt content is favorable to obtain high activity, which explains the efficiency of 0.05Pt/15Mo-TiO 2 . In summary, a series of Pt/Mo-TiO 2 catalysts with varying Pt and MoO 3 loadings were prepared for the hydrogenation of sulfur containing nitroarene. Systematic characterizations reveal that HxMoO 3 , formed via hydrogen spillover, serves as the active sites for NBZ hydrogenation and TiO 2 promotes interfacial hydrogen transfer from Pt to Mo. The optimal 0.05Pt/15Mo-TiO 2 achieved a conversion rate of 5448 h − 1 and excels with a broad range of nitroarene substrates. Shifting the hydrogenation site from noble metals to remote reducible metal oxides maximizes precious metal efficiency and improves sulfur tolerance. Both hydrogen spillover from Pt to MoO 3 and subsequent transfer to the nitro group govern the catalyst’s performance. These insights can guide the design of high-performance, sulfur-resistant catalysts that use minimal precious metals. Declarations Acknowledgments We are grateful for the financial support from the National Natural Science Foundation of China (No. 22472153, 22332002) and the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang (No. 2022R01007). 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Regulation of the Properties of Hydrogen Dissociation and Transfer in the Presence of S Atoms for Efficient Hydrogenations. ACS Catal. , 16214-16223 (2024). https://doi.org:10.1021/acscatal.4c05501 Liu, X. et al. Cooperation of Pt and TiOx in the Hydrogenation of Nitrobenzothiazole. ACS Catal. 12 , 11369-11379 (2022). https://doi.org:10.1021/acscatal.2c02988 Kuwahara, Y., Yoshimura, Y., Haematsu, K. & Yamashita, H. Mild Deoxygenation of Sulfoxides over Plasmonic Molybdenum Oxide Hybrid with Dramatic Activity Enhancement under Visible Light. J. Am. Chem. Soc. 140 , 9203-9210 (2018). https://doi.org:10.1021/jacs.8b04711 Touchy, A. S., Hakim Siddiki, S. M. A., Onodera, W., Kon, K. & Shimizu, K.-i. Hydrodeoxygenation of sulfoxides to sulfides by a Pt and MoOx co-loaded TiO 2 catalyst. Green Chem. 18 , 2554-2560 (2016). https://doi.org:10.1039/C5GC02806J Fan, S. et al. Subsurface Ru-Triggered Hydrogenation Capability of TiO 2–x Overlayer for Poison-Resistant Reduction of N-Heteroarenes. ACS Catal. 13 , 757-765 (2023). https://doi.org:10.1021/acscatal.2c04270 Cheng, H. et al. Hydrogen Doped Metal Oxide Semiconductors with Exceptional and Tunable Localized Surface Plasmon Resonances. J. Am. Chem. Soc. 138 , 9316-9324 (2016). https://doi.org:10.1021/jacs.6b05396 Kim, D. S., Kurusu, Y., Wachs, I. E., Hardcastle, F. D. & Segawa, K. Physicochemical properties of MoO 3 -TiO 2 prepared by an equilibrium adsorption method. J. Catal. 120 , 325-336 (1989). https://doi.org:https://doi.org/10.1016/0021-9517(89)90273-X Shetty, M., Murugappan, K., Prasomsri, T., Green, W. H. & Román-Leshkov, Y. Reactivity and stability investigation of supported molybdenum oxide catalysts for the hydrodeoxygenation (HDO) of m-cresol. J. Catal. 331 , 86-97 (2015). https://doi.org:https://doi.org/10.1016/j.jcat.2015.07.034 Lentz, C., Jand, S. P., Melke, J., Roth, C. & Kaghazchi, P. DRIFTS Study of CO Adsorption on Pt Nanoparticles Supported by DFT Calculations. J. Mol. Catal. A: Chem. 426 , 1-9 (2017). https://doi.org:https://doi.org/10.1016/j.molcata.2016.10.002 Panagiotopoulou, P. & Kondarides, D. I. Effects of Alkali Additives on the Physicochemical Characteristics and Chemisorptive Properties of Pt/TiO 2 Catalysts. J. Catal. 260 , 141-149 (2008). https://doi.org:https://doi.org/10.1016/j.jcat.2008.09.014 DeRita, L. et al. Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO 2 . J. Am. Chem. Soc. 139 , 14150-14165 (2017). https://doi.org:10.1021/jacs.7b07093 Tang, H. et al. Simultaneously Boosting Catalyst Activity and Stability by Construction of Low-Temperature Strong Metal−Support Interaction. ACS Catal. 14 (2024). https://doi.org:10.1021/acscatal.4c03421 Xin, H. et al. Overturning CO 2 Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions. J. Am. Chem. Soc. 144 , 4874-4882 (2022). https://doi.org:10.1021/jacs.1c12603 Schemes Scheme 1 is available in the Supplementary Files section Additional Declarations There is NO Competing Interest. Supplementary Files SI20250115.docx Experimental section, tables and characterization data Scheme1.png Scheme 1. Schematic diagram for catalytic machinery of Pt/Mo-TiO 2 catalyst (A) and summarized previous and current catalysts for the hydrogenation of sulfur-containing compounds (B). Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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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-5861758","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":408759179,"identity":"4dfc9981-cf9f-41b2-b7c2-d1455750fffe","order_by":0,"name":"Qihua Yang","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAs0lEQVRIiWNgGAWjYDACCTBpw8DYQKKWNNK1HCZaPQMD3+0ew88Fv87bM8/uMWD4uYMILZJ3zhhLz+y7zcw454wBY+8ZIrQY3MgxkObtuc3GOCPHgJmxjTgtxr95e87xkKTFTJrnxwEJ4rVI3kgrs+ZtSDZgnJFWcLCXGC18N5I33+b5Y2dvOCN544OfxGhhOMBhwAByj2EDkE2MBqAy9gcMDH8YGOSJUz4KRsEoGAUjEQAAalc2tJuSEbwAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0002-1118-3397","institution":"Zhejiang Normal University","correspondingAuthor":true,"prefix":"","firstName":"Qihua","middleName":"","lastName":"Yang","suffix":""},{"id":408759180,"identity":"fe5b4529-991f-4580-a11b-b640ca61038a","order_by":1,"name":"Zhenchao Zhao","email":"","orcid":"","institution":"Zhejiang Normal University","correspondingAuthor":false,"prefix":"","firstName":"Zhenchao","middleName":"","lastName":"Zhao","suffix":""},{"id":408759181,"identity":"b06daa02-ef7a-4207-9103-026372bc7fd4","order_by":2,"name":"Haitao Chen","email":"","orcid":"","institution":"Zhejiang Normal University","correspondingAuthor":false,"prefix":"","firstName":"Haitao","middleName":"","lastName":"Chen","suffix":""},{"id":408759182,"identity":"a7f6f694-f4a9-4bde-9e41-4d9e2c125f78","order_by":3,"name":"Zongpeng Ling","email":"","orcid":"","institution":"Zhejiang Normal University","correspondingAuthor":false,"prefix":"","firstName":"Zongpeng","middleName":"","lastName":"Ling","suffix":""},{"id":408759183,"identity":"f3e1a1cd-3c4b-4e3b-a2b7-cfff02d23a3b","order_by":4,"name":"Jie Yu","email":"","orcid":"","institution":"Zhejiang Normal University","correspondingAuthor":false,"prefix":"","firstName":"Jie","middleName":"","lastName":"Yu","suffix":""},{"id":408759184,"identity":"8299237e-92ba-4243-a199-bfca15ff1011","order_by":5,"name":"Tao Cheng","email":"","orcid":"","institution":"Zhejiang Normal University","correspondingAuthor":false,"prefix":"","firstName":"Tao","middleName":"","lastName":"Cheng","suffix":""},{"id":408759185,"identity":"80bcdaba-fe51-4e20-b7d9-f28116fa645c","order_by":6,"name":"Jingru Yang","email":"","orcid":"","institution":"Zhejiang Normal University","correspondingAuthor":false,"prefix":"","firstName":"Jingru","middleName":"","lastName":"Yang","suffix":""},{"id":408759186,"identity":"7a6d7985-3a5b-4a0c-86ff-fec8338b36d7","order_by":7,"name":"Xuefang Zhao","email":"","orcid":"","institution":"Zhejiang Normal University","correspondingAuthor":false,"prefix":"","firstName":"Xuefang","middleName":"","lastName":"Zhao","suffix":""},{"id":408759187,"identity":"23e2f8e0-4146-44f0-b5e8-5842a9ce6d3d","order_by":8,"name":"Yunuo Chen","email":"","orcid":"","institution":"Zhejiang Normal University","correspondingAuthor":false,"prefix":"","firstName":"Yunuo","middleName":"","lastName":"Chen","suffix":""},{"id":408759188,"identity":"2e99807c-e4dd-4630-98cb-f20220445816","order_by":9,"name":"Xin Liu","email":"","orcid":"","institution":"Dalian Institute of Chemical Physics","correspondingAuthor":false,"prefix":"","firstName":"Xin","middleName":"","lastName":"Liu","suffix":""}],"badges":[],"createdAt":"2025-01-20 01:35:16","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5861758/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5861758/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":75081100,"identity":"d321f41c-3762-48f5-a88d-3c6043339efc","added_by":"auto","created_at":"2025-01-30 08:56:21","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":232047,"visible":true,"origin":"","legend":"\u003cp\u003eInfluence of Mo and Pt loading. Reaction profiles (A) and conversion rate (B) of 0.05 wt% Pt supported on TiO\u003csub\u003e2\u003c/sub\u003e with different Mo loading and 15Mo-TiO\u003csub\u003e2\u003c/sub\u003e with different Pt loading for 5-nitrobenzothiazole hydrogenation. Reaction conditions: 80 °C, 2 MPa H\u003csub\u003e2\u003c/sub\u003e, S/C = 2000, 3 mL ethanol.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-5861758/v1/428e33de2a6e24ac7a52023b.png"},{"id":75080253,"identity":"39334f5e-b577-4eb3-8d7b-f61c275aee49","added_by":"auto","created_at":"2025-01-30 08:48:21","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":702005,"visible":true,"origin":"","legend":"\u003cp\u003ePt size and Ti, Mo, Pt element distribution. HAADF-STEM (A, B) EDS mapping (C-F) of 0.05Pt/15Mo-TiO\u003csub\u003e2 \u003c/sub\u003ecatalysts.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-5861758/v1/3dc203b067d6002bd26d5358.png"},{"id":75080256,"identity":"51c1a785-84a7-4a44-90bb-2bf4fb9fe694","added_by":"auto","created_at":"2025-01-30 08:48:21","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":367379,"visible":true,"origin":"","legend":"\u003cp\u003eStates of Mo and Pt. Mo 3d XPS spectra (A), FT-IR spectra of CO adsorbed (B) and H\u003csub\u003e2\u003c/sub\u003e-TPR profiles (C) of 0.05Pt/Mo-TiO\u003csub\u003e2 \u003c/sub\u003eand 0.05Pt/MoO\u003csub\u003e3\u003c/sub\u003e catalysts.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-5861758/v1/b8b058afa6788edc07d6b734.png"},{"id":75081320,"identity":"f096a4ce-26b6-45cb-afee-9e310a1855f1","added_by":"auto","created_at":"2025-01-30 09:04:21","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":180135,"visible":true,"origin":"","legend":"\u003cp\u003eMechanism investigation of the catalytic hydrogenation reaction. Correlation between intercalated H or Pt NPs density and conversion rate of Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e or Pt(C)/Mo-TiO\u003csub\u003e2\u003c/sub\u003e catalysts (A), reaction condition for Pt(C)/Mo-TiO\u003csub\u003e2\u003c/sub\u003e catalysts: 80 ºC, 2 MPa H\u003csub\u003e2\u003c/sub\u003e, 3 mg Cat, 10 mg NBZ, 3 mL ethanol.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-5861758/v1/49f53e83a0eb036cf2b16958.png"},{"id":80081059,"identity":"3899f9e5-2256-4344-ba03-20560e1c2966","added_by":"auto","created_at":"2025-04-07 15:48:44","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2094020,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5861758/v1/be68a1fa-13f9-4530-af86-51d893ae4ed9.pdf"},{"id":75081102,"identity":"331c4a2a-86bd-4242-a508-3cdbe1163bf1","added_by":"auto","created_at":"2025-01-30 08:56:21","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":4602606,"visible":true,"origin":"","legend":"Experimental section, tables and characterization data","description":"","filename":"SI20250115.docx","url":"https://assets-eu.researchsquare.com/files/rs-5861758/v1/d0dd5c7fb1af94410eac42e3.docx"},{"id":75080251,"identity":"c98d655d-1fcc-4617-acbf-713587b6c6b9","added_by":"auto","created_at":"2025-01-30 08:48:21","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":129763,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScheme 1.\u003c/strong\u003e Schematic diagram for catalytic machinery of Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e catalyst (A) and summarized previous and current catalysts for the hydrogenation of sulfur-containing compounds (B).\u003c/p\u003e","description":"","filename":"Scheme1.png","url":"https://assets-eu.researchsquare.com/files/rs-5861758/v1/c63fd0f6ab0e5345096cb6d2.png"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"\u003cp\u003eRegulation of Remote Sites to Enhance Pt Activity in the Hydrogenation of Sulfur-Containing Nitroarenes\u003c/p\u003e","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe outer-sphere catalysis involves remote interactions between catalysts and reactants, commonly observed in homogeneous catalysis, enzyme catalysis, and electrosynthesis.\u003csup\u003e\u003cspan additionalcitationids=\"CR2\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e In this mechanism, the metal center does not directly coordinate with the substrate but facilitates the reaction by altering the environment around the substrate molecule or providing a suitable reaction site. For instance, in outer-sphere hydrogenation catalysis, the substrate does not bind to the metal, and the catalyst transfers a hydride and a proton to the unbound substrate either through a concerted or stepwise pathway.\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e Outer-sphere pathways are, in principle, accessible to non-precious metals and even nonmetal catalysts, and they can also be applied to poison-resistant catalytic systems.\u003csup\u003e\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u003c/sup\u003e This reaction mechanism is typically found in enzyme catalysis and homogeneous catalysis, but has been rarely reported for heterogeneous catalysis.\u003csup\u003e\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e,\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eThe hydrogenation of sulfur-containing nitroarenes to their corresponding sulfur-containing anilines is of significant importance for practical applications, as these anilines serve as crucial intermediates in various pharmaceuticals.\u003csup\u003e\u003cspan additionalcitationids=\"CR8\" citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u003c/sup\u003e Developing robust catalysts with high resistance to sulfur poisoning is highly desirable for both fundamental research and practical applications. In heterogeneous catalysis, the hydrogenation of sulfur-containing compounds poses a significant challenge due to the strong coordination of sulfur atoms with metal sites, which greatly inhibits the activity of supported metal catalysts.\u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e,\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e,\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u003c/sup\u003e Several strategies have been proposed to enhance the sulfur resistance of supported metal catalysts for the hydrogenation of sulfur-containing compounds.\u003csup\u003e\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e Transition metal sulfides, such as NiMoS and CoMoS as industrial hydrodesulfurization catalysts, are intrinsically resistant to sulfur poisoning, but viable to desulfurization at high temperature due to its low hydrogenation activity.\u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e,\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e Recently, Glorius et al. discovered that noble metal sulfides, such as Ru-S catalysts with oxidized sulfur species, exhibit excellent performance in the hydrogenation of sulfur-containing quinolines to tetrahydroquinolines (THQs) under mild conditions.\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e Noble metals like Pd and Ru, when decorated with electron-rich atoms such as sulfur (S), phosphorus (P), or their related organic ligands, can effectively mitigate the poisoning effect of sulfur-containing substrates.\u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e,\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e,\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e These strategies primarily focus on modulating the surface structure of metal sites, and high metal loading is still required for the catalytic conversion of sulfur-containing compounds.\u003c/p\u003e \u003cp\u003eRecently, Pt/TiO\u003csub\u003e2\u003c/sub\u003e and Pt/MoO\u003csub\u003e3\u003c/sub\u003e catalysts were employed in the hydrogenation of 5-nitrobenzothiazole.\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e,\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e The results indicate that the oxygen vacancy (Ov) in Pt/TiO\u003csub\u003e2\u003c/sub\u003e and HxMoO\u003csub\u003e3\u003c/sub\u003e of Pt/MoO\u003csub\u003e3\u003c/sub\u003e serve as the actual hydrogenation sites. Similarly, Shimizu and colleagues found that the reduced Mo species were attributed to the active sites for hydrodeoxygenation in Pt-MoO\u003csub\u003e3\u003c/sub\u003e-catalyzed hydrodeoxygenation of sulfoxides to sulfides.\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e,\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e These examples highlight the in-situ generation of outer-sphere sites during hydrogenation and the critical role of hydrogen spillover. The in-situ formation of outer-sphere sites is closely associated with the strong metal-support interaction (SMSI) effect.\u003csup\u003e\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u003c/sup\u003e Generally, stronger SMSI promotes the formation of higher amounts of Ov or reduced Mo species but also leads to severe surface coverage of Pt, which restricts H\u003csub\u003e2\u003c/sub\u003e dissociation and hydrogen spillover. This contradiction limits the catalytic activity, necessitating high precious metal loading to achieve high conversion.\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e,\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e,\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e Therefore, the rational modulation of in-situ generated remote sites and hydrogen spillover is highly desirable to enhance the activity of supported metal catalysts and reduce the required amounts of precious metals in the hydrogenation of sulfur-containing compounds.\u003c/p\u003e \u003cp\u003eHerein, the in-situ generated remote sites (reduced Mo species) were precisely modulated using Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e as a model catalyst by controlling of the Pt-Mo/MoO\u003csub\u003e3\u003c/sub\u003e-TiO\u003csub\u003e2\u003c/sub\u003e interface (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The catalyst with 0.05 wt% Pt loading achieves the highest amounts of in-situ reduced Mo species and efficiently catalyzes the hydrogenation of 5-nitrobenzothiazole with a conversion rate of 5448 mol\u003csub\u003eNBZ\u003c/sub\u003e\u0026middot;mol\u003csub\u003ePt\u003c/sub\u003e⁻\u0026sup1;\u0026middot;h⁻\u0026sup1;, superior to previously reported catalysts. This is attributed to the optimized Pt density, which balances the stepwise H transfer from Pt to Mo and then to 5-nitrobenzothiazole. Detailed mechanism studies demonstrate the interfacial confined H transfer plays a crucial role in the enhanced catalytic performance.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eCatalyst preparation and screening\u003c/h2\u003e \u003cp\u003eMo-MO\u003csub\u003e2\u003c/sub\u003e (MO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;CeO\u003csub\u003e2\u003c/sub\u003e, SiO\u003csub\u003e2\u003c/sub\u003e, and ZrO\u003csub\u003e2\u003c/sub\u003e) supports were prepared by loading (NH\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e6\u003c/sub\u003eMo\u003csub\u003e7\u003c/sub\u003eO\u003csub\u003e24\u003c/sub\u003e.4H\u003csub\u003e2\u003c/sub\u003eO on MO\u003csub\u003e2\u003c/sub\u003e, followed by calcination in an air atmosphere at 550 \u0026deg;C. Pt was loaded onto MO\u003csub\u003e2\u003c/sub\u003e-TiO\u003csub\u003e2\u003c/sub\u003e, MoO\u003csub\u003e3\u003c/sub\u003e, and TiO\u003csub\u003e2\u003c/sub\u003e using the wet impregnation method with H\u003csub\u003e2\u003c/sub\u003e reduction. The BET surface areas of Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e catalysts are similar (ca. 24\u0026ndash;25 m\u003csup\u003e2\u003c/sup\u003e/g), slightly lower than that of Pt/TiO\u003csub\u003e2\u003c/sub\u003e (33 m\u003csup\u003e2\u003c/sup\u003e/g) but significantly higher than Pt/MoO\u003csub\u003e3\u003c/sub\u003e (2 m\u003csup\u003e2\u003c/sup\u003e/g, Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e). The Mo and Pt contents were determined to range from 0 to 20 wt% and 0.05 to 1 wt%, respectively. The BET surface area of control catalysts, 0.1Pt/5Mo-CeO\u003csub\u003e2\u003c/sub\u003e, 0.1Pt/5Mo-ZrO\u003csub\u003e2\u003c/sub\u003e and 0.1Pt/5Mo-SiO\u003csub\u003e2\u003c/sub\u003e with 0.1 wt% Pt and 5 wt% MoO\u003csub\u003e3\u003c/sub\u003e loading is in the range of 14\u0026ndash;209 m\u003csup\u003e2\u003c/sup\u003e/g (Table S2). In the hydrogenation of 5-nitrobenzothiazole (NBZ), 0.1Pt/5Mo-CeO\u003csub\u003e2\u003c/sub\u003e and 0.1Pt/5Mo-ZrO\u003csub\u003e2\u003c/sub\u003e are almost inactive, while 0.1Pt/5Mo-SiO\u003csub\u003e2\u003c/sub\u003e showed 13% conversion (Table S2). To our delight, almost full conversion with \u0026gt;\u0026thinsp;99% selectivity to aminobenzothiazole (ABZ) was achieved over 0.1Pt/5Mo-TiO\u003csub\u003e2\u003c/sub\u003e under the similar conditions. These results demonstrate that 0.1Pt/5Mo-TiO\u003csub\u003e2\u003c/sub\u003e is an efficient catalyst for the hydrogenation of NBZ.\u003c/p\u003e \u003cp\u003eInspired by the high activity of 0.1Pt/5Mo-TiO\u003csub\u003e2\u003c/sub\u003e, the Mo and Pt loadings were further optimized. The reaction profiles (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eA) reveal that all Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e catalysts exhibit higher activity than Pt/TiO\u003csub\u003e2\u003c/sub\u003e. Over similar time intervals, the conversion increases as the Mo content in the catalysts rises, peaking at 15 wt% Mo, which achieves complete NBZ conversion within just 30 minutes. However, the conversion declines as the Mo loading further increases to 20 wt%, with a more pronounced decrease observed when pure MoO\u003csub\u003e3\u003c/sub\u003e is used as the support. As the Mo loading increases, the conversion rate (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eB) gradually rises, reaching a maximum of 5448 mol\u003csub\u003eNBZ\u003c/sub\u003e\u0026middot;mol\u003csub\u003ePt\u003c/sub\u003e\u003csup\u003e\u0026minus;1\u003c/sup\u003e\u0026middot;h\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e at 15 wt% Mo, before decreasing with further increase of Mo loading. Compared to Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e catalysts, Pt/MoO\u003csub\u003e3\u003c/sub\u003e and Pt/TiO\u003csub\u003e2\u003c/sub\u003e exhibit relatively lower activity. The activity sequence follows the order: 0.05Pt/MoO\u003csub\u003e3\u003c/sub\u003e\u0026thinsp;\u0026lt;\u0026thinsp;0.05Pt/TiO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;\u0026lt;\u0026thinsp;0.05Pt/5Mo-TiO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;\u0026lt;\u0026thinsp;0.05Pt/10Mo-TiO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;\u0026lt;\u0026thinsp;0.05Pt/20Mo-TiO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;\u0026lt;\u0026thinsp;0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e. These results clearly demonstrate that the presence of MoO\u003csub\u003e3\u003c/sub\u003e significantly enhances the performance of Pt/TiO\u003csub\u003e2\u003c/sub\u003e, with the optimal Mo loading being 15 wt%. Furthermore, the catalytic performance of Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e catalysts is strongly influenced by the amount of Pt present on the catalysts. The activity of Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e decreases sharply as the Pt loading increases. The reaction rate of 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e is approximately 20 times that of 1Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e. Compared to previously reported catalysts (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e), the precious metal loading of 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e is the lowest required to achieve high conversion in the hydrogenation of sulfur-containing compounds.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eCatalyst characterization\u003c/h3\u003e\n\u003cp\u003eTo identify the key factors affecting the catalytic performance, the supported Pt catalysts were fully characterized. The XRD and Raman characterization results (Figure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003eA-B) reveal that only characteristic peaks assigned to rutile TiO\u003csub\u003e2\u003c/sub\u003e could be observed for all Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e catalysts, demonstrating that Mo species are likely highly dispersed as a monolayer or in a few layers on the TiO\u003csub\u003e2\u003c/sub\u003e support. The signals of TiO\u003csub\u003e2\u003c/sub\u003e at 239, 447 and 610 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e decrease significantly after Mo loading in the Raman spectra of Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e, implying the surface coverage of TiO\u003csub\u003e2\u003c/sub\u003e by Mo species (Figure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003eB).\u003csup\u003e\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e,\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e For 0.05Pt/MoO\u003csub\u003e3\u003c/sub\u003e, distinct MoO\u003csub\u003e3\u003c/sub\u003e signals are clearly visible. Transmission electron microscopy (TEM) and high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) images show the existence of Pt nanoparticles ranging from 1.1 to 3.6 nm in size on the catalysts (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eA and S2). From 0.05 Pt/TiO\u003csub\u003e2\u003c/sub\u003e to 0.05Pt/5Mo-TiO\u003csub\u003e2\u003c/sub\u003e and then to 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e, the Pt size gradually decreases from 2.1 to 1.5 and then to 1.1 nm, indicating that MoO\u003csub\u003e3\u003c/sub\u003e promotes Pt dispersion. 1Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e exhibits a relatively larger Pt size of 3.6 nm. Corresponding energy dispersive spectroscopy (EDS) elemental mapping images show the uniform distribution of Mo on TiO\u003csub\u003e2\u003c/sub\u003e and the preferential location of Pt on MoO\u003csub\u003e3\u003c/sub\u003e, suggesting close contact between Pt and Mo (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eC-F).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eOnly reduced Mo species including Mo\u003csup\u003e5+\u003c/sup\u003e(232.0 eV), Mo\u003csup\u003e4+\u003c/sup\u003e(231.0 eV), and Mo\u003csup\u003e3+\u003c/sup\u003e(229.5 eV) \u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e are observed in the Mo 3d X-ray photoelectron spectroscopy (XPS) spectra of Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eA), with Mo\u003csup\u003e5+\u003c/sup\u003e and Mo\u003csup\u003e4+\u003c/sup\u003e being dominant. The relative ratio of Mo\u003csup\u003e3+\u003c/sup\u003e increases as the Mo loading rises from 5 to 20 wt% for 0.05Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e (Table S3). This indicates the complete reduction of MoO\u003csub\u003e3\u003c/sub\u003e during the catalyst preparation process and a deeper Mo reduction degree at higher MoO\u003csub\u003e3\u003c/sub\u003e loading, which may be associated with the stronger interaction between TiO\u003csub\u003e2\u003c/sub\u003e and MoO\u003csub\u003e3\u003c/sub\u003e at lower MoO\u003csub\u003e3\u003c/sub\u003e loading. With Pt loading increasing to 1 wt%, a slight increase in the ratios of Mo\u003csup\u003e4+\u003c/sup\u003e and Mo\u003csup\u003e3+\u003c/sup\u003e was observed for 1Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e compared to 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e. In addition to Mo\u003csup\u003e5+\u003c/sup\u003e and Mo\u003csup\u003e4+\u003c/sup\u003e, the presence of Mo\u003csup\u003e6+\u003c/sup\u003e (232.0 eV) with a relative ratio of 34% was clearly observed in the Mo 3d XPS spectrum of 0.05Pt/MoO\u003csub\u003e3\u003c/sub\u003e. No Mo\u003csup\u003e3+\u003c/sup\u003e were detected for 0.05Pt/MoO\u003csub\u003e3\u003c/sub\u003e, indicating that the formation of reduced Mo species can be efficiently modulated by loading MoO\u003csub\u003e3\u003c/sub\u003e on TiO\u003csub\u003e2\u003c/sub\u003e.\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e O1s XPS spectra (Figure S3A and Table S4) of Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e show signals of bulk O of TiO\u003csub\u003e2\u003c/sub\u003e at 530.4 eV and hydroxyl O at 531.6 eV, arising from the reduction of MoO\u003csub\u003e3\u003c/sub\u003e due to hydrogen spillover.\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e The relative amount of hydroxyl increases as the Mo content and reaches a maximum at 15 wt% Mo loading, while no apparent changes were observed for 1Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e with increased Pt loading (Table S4). Substantial hydroxyl O species can also be observed for Pt/MoO\u003csub\u003e3\u003c/sub\u003e probably due to the formation of bulk HxMoO\u003csub\u003e3\u003c/sub\u003e near the surface. The binding energies of Pt 4f\u003csub\u003e7/2\u003c/sub\u003e gradually increase from 70.8 to 71.5 eV as Mo loading increases from 0 wt% to 100 wt% for 0.05Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e. Similar increase in binding energy of Pt 4f\u003csub\u003e7/2\u003c/sub\u003e to 71.3 eV was also observed for 1Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e (Table S4), suggesting the electron transfer from Pt to Mo.\u003c/p\u003e \u003cp\u003eThe FT-IR spectra of CO adsorption on 0.05 wt% Pt loaded on Mo-TiO\u003csub\u003e2\u003c/sub\u003e, TiO\u003csub\u003e2\u003c/sub\u003e and MoO\u003csub\u003e3\u003c/sub\u003e were collected to explore the effect of Mo on the status of Pt (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eB). A strong broad absorption band at 2071 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e assigned to CO adsorbed at the edge/corner of Pt NPs, along with weak signal of CO on Pt\u003csup\u003eδ+\u003c/sup\u003e at 2100 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and bridge-adsorbed CO near 1850 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, were observed for 0.05Pt/TiO\u003csub\u003e2\u003c/sub\u003e.\u003csup\u003e25\u0026ndash;27\u003c/sup\u003e All 0.05Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e catalysts also display major CO adsorbed at the edge/corner of Pt NPs, but the bridge-adsorbed CO disappeared. The edge/corner adsorbed CO band blue-shifted accompanied with the reduction in band intensity for 0.05Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e as the MoO\u003csub\u003e3\u003c/sub\u003e loading increased, which may be attributed to a pronounced SMSI effect.\u003csup\u003e28\u003c/sup\u003e 1Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e (Figure S4) also shows edge/corner adsorbed CO with substantial reduction in peak intensity. No CO absorption band could be observed in the FT-IR spectrum of 0.05Pt/MoO\u003csub\u003e3\u003c/sub\u003e, indicating the sever surface coverage of Pt due to the SMSI.\u003csup\u003e\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn the H\u003csub\u003e2\u003c/sub\u003e-TPR profiles (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eC and Figure S5), the reduction peaks below 200\u0026deg;C can be assigned to hydrogen intercalation into MoO\u003csub\u003e3\u003c/sub\u003e matrixes to form HxMoO\u003csub\u003e3\u003c/sub\u003e, and weak H\u003csub\u003e2\u003c/sub\u003e consumption peaks between 200 to 300 \u0026ordm;C are attributed to the formation of molybdenum suboxides (e.g., Mo\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e11\u003c/sub\u003e or MoO\u003csub\u003e3\u0026thinsp;\u0026minus;\u0026thinsp;x\u003c/sub\u003e).\u003csup\u003e19,29\u003c/sup\u003e 15Mo-TiO\u003csub\u003e2\u003c/sub\u003e shows a MoO\u003csub\u003e3\u003c/sub\u003e reduction peak near 390\u0026deg;C (Figure S5), much lower than MoO\u003csub\u003e3\u003c/sub\u003e (above 500 \u0026ordm;C), \u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e,\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u003c/sup\u003e indicating that TiO\u003csub\u003e2\u003c/sub\u003e promotes MoO\u003csub\u003e3\u003c/sub\u003e reduction. The lower temperature of the reduction peaks of Pt/MoTiO\u003csub\u003e2\u003c/sub\u003e and Pt/MoO\u003csub\u003e3\u003c/sub\u003e than those of MoO\u003csub\u003e3\u003c/sub\u003e and MoTiO\u003csub\u003e2\u003c/sub\u003e suggests that Pt facilitates Mo reduction. Pt/MoTiO\u003csub\u003e2\u003c/sub\u003e with Mo loading below 15 wt% mainly exhibits reduction peaks below 200\u0026deg;C, and that with \u0026ge;\u0026thinsp;15 wt% Mo shows both low- and high-temperature peaks, indicating that HxMoO\u003csub\u003e3\u003c/sub\u003e species and molybdenum suboxides coexist in Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e with Mo loading\u0026thinsp;\u0026ge;\u0026thinsp;15 wt%, while 0.05Pt/5Mo-TiO\u003csub\u003e2\u003c/sub\u003e and 0.05Pt/10Mo-TiO\u003csub\u003e2\u003c/sub\u003e contain only HxMoO\u003csub\u003e3\u003c/sub\u003e. Compared to 0.05Pt/MoO\u003csub\u003e3\u003c/sub\u003e, 0.05Pt/MoTiO\u003csub\u003e2\u003c/sub\u003e shows a lower-temperature reduction peak, possibly due to the high dispersion of MoO\u003csub\u003e3\u003c/sub\u003e on TiO\u003csub\u003e2\u003c/sub\u003e.\u003csup\u003e23\u003c/sup\u003e The reduction peak of 1Pt/15MoTiO\u003csub\u003e2\u003c/sub\u003e assigned to the formation of HxMoO\u003csub\u003e3\u003c/sub\u003e further moves down to 32\u0026deg;C, much lower than that of 0.05Pt/15MoTiO\u003csub\u003e2\u003c/sub\u003e, implying much easier hydrogen intercalation into MoO\u003csub\u003e3\u003c/sub\u003e at higher Pt loading (Figure S5). The H\u003csub\u003e2\u003c/sub\u003e consumption amounts assigned to the formation of HxMoO\u003csub\u003e3\u003c/sub\u003e increases from 0.05Pt/5Mo-TiO\u003csub\u003e2\u003c/sub\u003e to 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e, and then decreases for 0.05Pt/20Mo-TiO\u003csub\u003e2\u003c/sub\u003e (Table S5). It is interesting to mention that 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e and 1Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e have similar intercalated H contents (3.4 versus 3.7 mmol/g), verifying that ppm Pt is enough for the formation of substantial amounts of HxMoO\u003csub\u003e3\u003c/sub\u003e.\u003c/p\u003e\n\u003ch3\u003eActive sites identification\u003c/h3\u003e\n\u003cp\u003ePrevious results suggest that HxMoO\u003csub\u003e3\u003c/sub\u003e of Pt/MoO\u003csub\u003e3\u003c/sub\u003e mainly serve as active sites for the hydrogenation of sulfur-containing compounds.\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e,\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u003c/sup\u003e To identify the active sites involved in our catalysts, H\u003csub\u003e2\u003c/sub\u003e activated 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e and 0.05Pt/MoO\u003csub\u003e3\u003c/sub\u003e were used for NBZ hydrogenation under N\u003csub\u003e2\u003c/sub\u003e atmosphere (Figure S6). As expected, the product ABZ was detected for both samples, showing that HxMoO\u003csub\u003e3\u003c/sub\u003e acts as remote active sites for NBZ hydrogenation. Combined with H\u003csub\u003e2\u003c/sub\u003e consumption amounts from H\u003csub\u003e2\u003c/sub\u003e-TPR, about 50% and 10% stored H in HxMoO\u003csub\u003e3\u003c/sub\u003e of 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e and 0.05Pt/MoO\u003csub\u003e3\u003c/sub\u003e could be transferred to NBZ, respectively. The conversion rate per Pt atom of 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e is approximately 1.6 folds that of 0.05Pt/MoO\u003csub\u003e3\u003c/sub\u003e though the later has more than 5 folds HxMoO\u003csub\u003e3\u003c/sub\u003e than the former according to H\u003csub\u003e2\u003c/sub\u003e-TPR. This implies that the H species of HxMoO\u003csub\u003e3\u003c/sub\u003e in 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e is more efficiently transferred to NBZ than those in 0.05Pt/MoO\u003csub\u003e3\u003c/sub\u003e, possibly due to the high dispersion of MoO\u003csub\u003e3\u003c/sub\u003e on TiO\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e \u003cp\u003eConsidering that HxMoO\u003csub\u003e3\u003c/sub\u003e is the active sites for NBZ hydrogenation, the activity of 0.05Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e was related with amounts of intercalated H obtained from H\u003csub\u003e2\u003c/sub\u003e-TPR. A linear correlation was observed, further confirming that in situ formed surface HxMoO\u003csub\u003e3\u003c/sub\u003e is the main active site for NBZ hydrogenation (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eA). The substantial deviation of 0.05Pt/MoO\u003csub\u003e3\u003c/sub\u003e likely arises from a combination of surface coverage by Pt nanoparticles due to strong SMSI and the limited exposure of bulk HxMoO\u003csub\u003e3\u003c/sub\u003e. 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e and 1Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e with similar amounts of intercalated H exhibit different activities at identical NBZ/Pt ratio or at similar catalyst weight (Figure S7). Because the two catalysts have different Pt size, Pt(C)/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e catalysts were prepared by loading different amounts of ~\u0026thinsp;2 nm Pt colloids on 15Mo-TiO\u003csub\u003e2\u003c/sub\u003e to exclude the influence of Pt size and investigate the role of Pt. The TEM images show that Pt(C)/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e with Pt loading in the range of 0.05 wt% to 2 wt% have similar Pt size of about 2.0 nm (Figure S8). When tested for NBZ hydrogenation under the same catalyst mass, the per-Pt-atom activity of Pt(C)/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e decreased from 1884 to 274 mol\u003csub\u003eNBZ\u003c/sub\u003e\u0026middot;mol\u003csub\u003ePt\u003c/sub\u003e⁻\u0026sup1;\u0026middot;h⁻\u0026sup1; as Pt loading increased, mirroring the trend in 0.05Pt/xMo-TiO\u003csub\u003e2\u003c/sub\u003e. In this case, varying the Pt content only changed the density of Pt NPs on the catalysts, thus, the number of Pt NPs per 1 x 10\u003csup\u003e4\u003c/sup\u003e nm\u0026sup2; was calculated and corelated with the activity of Pt(C)/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eA). 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e with low Pt density (three Pt nanoparticles per 1 x 10\u003csup\u003e4\u003c/sup\u003e nm\u0026sup2;) achieved the highest activity. This suggests that low Pt density favored HxMoO\u003csub\u003e3\u003c/sub\u003e mediated sequential H transfer from Pt to Mo and subsequently to the substrate. Higher Pt density may enhance H transfer to Mo, but the hydrogenation process becomes limited by the availability of HxMoO\u003csub\u003e3\u003c/sub\u003e for further H transfer to the substrate, revealing the intrinsic reason for the high activity of 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e with ppm Pt.\u003c/p\u003e\n\u003ch3\u003eReaction mechanism investigation\u003c/h3\u003e\n\u003cp\u003eDirect hydrogen transfer from Pt to NBZ is hindered by NBZ\u0026rsquo;s strong adsorption on the Pt surface. This was confirmed by testing the activity of 0.05Pt/TiO\u003csub\u003e2\u003c/sub\u003e and 0.05Pt/15Mo\u0026ndash;TiO\u003csub\u003e2\u003c/sub\u003e in nitrobenzene (NB) hydrogenation to aniline (AN) in the presence and absence of the sulfur poison benzothiazole (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eB). Although 0.05Pt/TiO\u003csub\u003e2\u003c/sub\u003e initially achieves a high reaction rate of 26522 mol\u003csub\u003eAN\u003c/sub\u003e\u0026middot;mol\u003csub\u003ePt\u003c/sub\u003e⁻\u0026sup1;\u0026middot;h⁻\u0026sup1;, it drops to 291 mol\u003csub\u003eAN\u003c/sub\u003e\u0026middot;mol\u003csub\u003ePt\u003c/sub\u003e⁻\u0026sup1;\u0026middot;h⁻\u0026sup1; (nearly 99% loss) with benzothiazole, indicating that the sulfur-induced Pt site blockage impedes direct H transfer. In contrast, 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e retains 60% of its activity (falling from 15913 to 9753 mol\u003csub\u003eAN\u003c/sub\u003e\u0026middot;mol\u003csub\u003ePt\u003c/sub\u003e⁻\u0026sup1;\u0026middot;h⁻\u0026sup1;), attributed to the existence of large amounts of remote sites. These findings confirm the H transfer from Pt to Mo and subsequently to NBZ.\u003c/p\u003e \u003cp\u003eKinetic studies with 0.05Pt/TiO\u003csub\u003e2\u003c/sub\u003e, 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e, and 1.0Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e (Figs.\u0026nbsp;5C-D) reveal similar hydrogen reaction orders (0.54\u0026ndash;0.68). However, 0.05Pt/TiO\u003csub\u003e2\u003c/sub\u003e shows a more negative NBZ reaction order (-0.75) than the Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e catalysts (in the range of -0.36 to -0.45), implying stronger NBZ adsorption on Pt/TiO\u003csub\u003e2\u003c/sub\u003e. The r\u003csub\u003eH2\u003c/sub\u003e/r\u003csub\u003eD2\u003c/sub\u003e ratio is 1.4\u0026ndash;1.6 for all catalysts (Fig.\u0026nbsp;5E), but a distinct kinetic isotope effect (KIE) appears with the solvent. The r\u003csub\u003eEtOH\u003c/sub\u003e/r\u003csub\u003eEtOD\u003c/sub\u003e ratios are 2.4, 1.0, and 0.7 for 0.05Pt/TiO\u003csub\u003e2\u003c/sub\u003e, 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e, and 1Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e, respectively, indicating different H transfer route for the catalysts. The strong solvent KIE with Pt/TiO\u003csub\u003e2\u003c/sub\u003e suggests that protons of solvent are actively participating in the reaction, potentially involving hydrogen spillover through proton-coupled electron transfer during the hydrogenation process, which is further confirmed by the higher activity of 0.05Pt/TiO\u003csub\u003e2\u003c/sub\u003e in ethanol than in toluene in NBZ hydrogenation (Fig.\u0026nbsp;5e). For Pt/15Mo-TiO₂, the transfer of H from Pt to 15Mo-TiO\u003csub\u003e2\u003c/sub\u003e, and subsequently to substrate may occur directly through HxMoO\u003csub\u003e3\u003c/sub\u003e matrix. The similar activity of 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e in ethanol and toluene further confirms the direct H transfer via HxMoO\u003csub\u003e3\u003c/sub\u003e.\u003c/p\u003e \u003cp\u003e\u003cimg 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\" width=\"809\" height=\"483\"\u003e\u003c/p\u003e \u003cp\u003e0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e also demonstrated excellent activity and selectivity across a broad range of nitroarenes (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e), achieving up to \u0026gt;94% conversion with \u0026gt;98% selectivity to nitro hydrogenated products while tolerating chlorides, olefins, and other functionalized aromatics. It also exhibited strong sulfur resistance, efficiently hydrogenating mercaptans and thioethers within 1 hour at S/C ratios above 2000. In a continuous flow reactor (Figure S9), Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e catalyst maintained a stable conversion rate at 118 mol\u003csub\u003eNBZ\u003c/sub\u003e\u0026middot;mol\u003csub\u003ePt\u003c/sub\u003e⁻\u0026sup1;\u0026middot;h⁻\u0026sup1; over 25 h, with a slight decrease to 97 mol\u003csub\u003eNBZ\u003c/sub\u003e\u0026middot;mol\u003csub\u003ePt\u003c/sub\u003e⁻\u0026sup1;\u0026middot;h⁻\u0026sup1; after 75 hours. In comparison, the 0.05Pt/MoO\u003csub\u003e3\u003c/sub\u003e catalyst exhibited a sharp decrease in conversion rate, dropping from 45 to 18 mol\u003csub\u003eNBZ\u003c/sub\u003e\u0026middot;mol\u003csub\u003ePt\u003c/sub\u003e⁻\u0026sup1;\u0026middot;h⁻\u0026sup1; within 75 hours.\u003c/p\u003e\n\u003ch3\u003eDiscussion\u003c/h3\u003e\n\u003cp\u003eIn the hydrogenation of sulfur containing compounds, the catalysts are often required to have high content of precious metal to achieve desirable conversion, due to the poisoning effect of sulfur atom. In this work, it was found that 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e with minim Pt content shows high activity in the hydrogenation of NBZ. The efficient conversion of NBZ over H\u003csub\u003e2\u003c/sub\u003e treated 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e in N\u003csub\u003e2\u003c/sub\u003e shows that HxMoO\u003csub\u003e3\u003c/sub\u003e is active site for NBZ hydrogenation, demonstrating the importance in the regulation of remote sites. The almost linear relationship of activity and HxMoO\u003csub\u003e3\u003c/sub\u003e of 0.05Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e suggests that higher amounts of HxMoO\u003csub\u003e3\u003c/sub\u003e are favorable for the high activity. However, a contradiction was observed for 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e and 1Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e, showing that the amounts of HxMoO\u003csub\u003e3\u003c/sub\u003e are not the only factor influencing the activity. Pt(C)/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e with similar Pt size but different Pt content was employed to investigate the role of Pt content in the hydrogenation of NBZ. It was found that the reaction rate decreases with the Pt content increasing. The optimized Pt density is three Pt NPs/1x 10\u003csup\u003e4\u003c/sup\u003e nm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e, showing the important role of Pt/surface Mo ratio. In the hydrogenation of NBZ, the H\u003csub\u003e2\u003c/sub\u003e is dissociated on Pt NPs, the dissociated H intercalated into MoO\u003csub\u003e3\u003c/sub\u003e to form HxMoO\u003csub\u003e3\u003c/sub\u003e, then the product was formed by transferring H from HxMoO\u003csub\u003e3\u003c/sub\u003e to NBZ. When the H transfer rate from HxMoO\u003csub\u003e3\u003c/sub\u003e to NBZ is slower than the formation rate of HxMoO\u003csub\u003e3\u003c/sub\u003e, the H transfer from Pt to MoO\u003csub\u003e3\u003c/sub\u003e should be inhibited, as a result, lower Pt content is favorable to obtain high activity, which explains the efficiency of 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e \u003cp\u003eIn summary, a series of Pt/Mo-TiO\u003csub\u003e2\u003c/sub\u003e catalysts with varying Pt and MoO\u003csub\u003e3\u003c/sub\u003e loadings were prepared for the hydrogenation of sulfur containing nitroarene. Systematic characterizations reveal that HxMoO\u003csub\u003e3\u003c/sub\u003e, formed via hydrogen spillover, serves as the active sites for NBZ hydrogenation and TiO\u003csub\u003e2\u003c/sub\u003e promotes interfacial hydrogen transfer from Pt to Mo. The optimal 0.05Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e achieved a conversion rate of 5448 h\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and excels with a broad range of nitroarene substrates. Shifting the hydrogenation site from noble metals to remote reducible metal oxides maximizes precious metal efficiency and improves sulfur tolerance. Both hydrogen spillover from Pt to MoO\u003csub\u003e3\u003c/sub\u003e and subsequent transfer to the nitro group govern the catalyst\u0026rsquo;s performance. These insights can guide the design of high-performance, sulfur-resistant catalysts that use minimal precious metals.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAcknowledgments\u003c/h2\u003e \u003cp\u003eWe are grateful for the financial support from the National Natural Science Foundation of China (No. 22472153, 22332002) and the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang (No. 2022R01007).\u003c/p\u003e\u003ch2\u003eSupporting information\u003c/h2\u003e \u003cp\u003eExperimental section, table of Pt and Mo content, surface areas, table of summarized catalytic performance of various Pt/Mo-based catalysts for NBZ hydrogenation, XRD patterns, Raman spectra, IR spectra of CO adsorption, TEM and EDS mapping images, XPS, catalytic performance of Pt/15Mo-TiO\u003csub\u003e2\u003c/sub\u003e with various Pt contents, and time on stream reaction profiles for stability test are available in the supporting information.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eEisenstein, O. \u0026amp; Crabtree, R. 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Soc.\u003c/em\u003e \u003cstrong\u003e144\u003c/strong\u003e, 4874-4882 (2022). https://doi.org:10.1021/jacs.1c12603\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Schemes","content":"\u003cp\u003eScheme 1 is available in the Supplementary Files section\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","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":"Remote site, sulfur-containing compounds, hydrogenation, hydrogen spillover, strong metal support interaction","lastPublishedDoi":"10.21203/rs.3.rs-5861758/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5861758/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eOuter-sphere catalysis, commonly associated with enzyme catalysis and homogeneous catalysis, utilizes remote sites to drive reactions and is particularly effective for reactants that are toxic to the catalyst. However, this approach has been rarely explored in heterogeneous catalysis. In this study, we demonstrate the use of remote sites to enhance the activity of Pt nanoparticles (NPs) in the hydrogenation of sulfur-containing nitroarenes. Catalysts with Pt and MoO\u003csub\u003e3\u003c/sub\u003e co-deposited on TiO\u003csub\u003e2\u003c/sub\u003e efficiently catalyze the hydrogenation of 5-nitrobenzothiazole (NBZ) under mild conditions, achieving a conversion rate of 5448 mol\u003csub\u003eNBZ\u003c/sub\u003e \u0026middot; mol\u003csub\u003ePt\u003c/sub\u003e⁻\u0026sup1; \u0026middot; h⁻\u0026sup1;, the highest reported to date, even with ppm levels of Pt. The optimized Pt density (~\u0026thinsp;3 NPs per 1\u0026times;10\u003csup\u003e4\u003c/sup\u003e nm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e) on the catalyst was found to favor HxMoO\u003csub\u003e3\u003c/sub\u003e mediated sequential H transfer from Pt to Mo and subsequently to the substrate. Higher Pt density may enhance H transfer to Mo, but the hydrogenation process becomes limited by the availability of HxMoO\u003csub\u003e3\u003c/sub\u003e for further H transfer to the substrate, revealing the intrinsic reason for the high activity of catalysts with ppm Pt. A direct H transfer pathway via HxMoO\u003csub\u003e3\u003c/sub\u003e to the substrate, rather than solvent-mediated proton-coupled electron transfer, was observed and confirmed through solvent isotope kinetic effects and solvent studies. Tuning remote sites on solid catalysts offers a promising strategy for developing catalysts with the minim use of precious metals in the hydrogenation of strongly coordinating reactants.\u003c/p\u003e","manuscriptTitle":"Regulation of Remote Sites to Enhance Pt Activity in the Hydrogenation of Sulfur-Containing Nitroarenes","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-01-30 08:48:16","doi":"10.21203/rs.3.rs-5861758/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","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":"445edd60-6c13-4252-904f-1d77a8535b3c","owner":[],"postedDate":"January 30th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":43609690,"name":"Physical sciences/Chemistry/Catalysis/Heterogeneous catalysis"},{"id":43609691,"name":"Physical sciences/Chemistry/Green chemistry/Sustainability"}],"tags":[],"updatedAt":"2025-04-07T15:40:35+00:00","versionOfRecord":[],"versionCreatedAt":"2025-01-30 08:48:16","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-5861758","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5861758","identity":"rs-5861758","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}