Spatial-Confinement in Biomimetic Catalysts: Enhancing Homolytic Sulfur-Chain Reactions and Enzyme-like Activity for High-Performance Lithium-Sulfur Batteries

Spatial-Confinement in Biomimetic Catalysts: Enhancing Homolytic Sulfur-Chain Reactions and Enzyme-like Activity for High-Performance Lithium-Sulfur Batteries | 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 Spatial-Confinement in Biomimetic Catalysts: Enhancing Homolytic Sulfur-Chain Reactions and Enzyme-like Activity for High-Performance Lithium-Sulfur Batteries Dong Cai, Tingting Li, Yang Dong, Zeyi Guo, Shuo Yang, meiling Shu, and 5 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4727879/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 The most burning issue for high-energy-density lithium-sulfur batteries is developing high-efficient catalyst to address sulfur reaction kinetics and lithium polysulfide shuttling effects. In this work, we present Fe-TCPP@Cu-BTC, a biomimetic catalyst that mimics cytochrome c oxidase, by encapsulating porphyrin-based small molecules into metal-organic frameworks, for high-performance lithium-sulfur batteries. Through a series of in-situ spectroscopic analyses and theoretical simulations, it was found that the Cu-Fe bimetallic center within the spatially confined Fe-TCPP@Cu-BTC significantly promotes the homolytic cleavage of Li 2 S 6 to LiS 3 , and accelerates their subsequent conversion to Li 2 S. The enzyme-like properties were further evaluated using Michaelis-Menten kinetics, confirming that the homolytic reaction can increase the sulfur conversion rate by nearly 100-fold. As a result, the pouch lithium-sulfur batteries delivered an energy density exceeding 300 Wh/kg. This work demonstrates the tremendous potential of component and structural regulation of biomimetic enzymes in the conversion reactions of metal-sulfur batteries. Physical sciences/Chemistry/Electrochemistry/Batteries Physical sciences/Chemistry/Catalysis/Electrocatalysis lithium − sulfur battery iron porphyrin metal-organic-framework spatial confinement enzymatic catalysis lithium polysulfide homolytic reaction Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 1. Introduction Lithium-sulfur batteries (LSBs), positioned as the next frontier in energy storage technology, offer several distinct advantages over traditional lithium-ion batteries: superior energy density (2600 Wh kg − 1 ), cost-effective, and reduced environmental impact, all of which suggest potential for scalable and significantly longer-lasting power sources 1 – 3 . The functioning of LSBs entails the gradual decomposition of S 8 rings, resulting in the formation of both long-chain and short-chain lithium polysulfides (LiPSs) upon interaction with Li + , and ultimately culminates in the production of lithium sulfide (Li 2 S) end products 4 – 6 . Nevertheless, LSBs still face several challenges including slow sulfur redox reactions and severe LiPS shuttle effects between the S cathode and the Li anode 7 – 9 . These issues become particularly critical in practical applications, primarily due to LiPS accumulation under conditions of high sulfur loading and limited electrolyte addition. This accumulation results in severe parasitic reactions at the Li anode, over-saturation precipitation of Li 2 S, and low sulfur utilization efficiency, ultimately impacting the energy density and lifespan of LSBs 1 , 10 – 12 . Developing efficient electrocatalytic materials to expedite the conversion of LiPSs represents a promising approach for tackling the aforementioned challenges 13 . A prevalent method in this pursuit involves integrating highly conductive carbon materials with metal oxides 14 , 15 , phosphides 16 , sulfides 17 , or nitrides 18 to establish catalytic centers. These centers facilitate the rapid conversion of LiPSs into insoluble Li 2 S 2 /Li 2 S at the conductive solid-liquid interface, thereby achieving high sulfur conversion rate 19 . However, the efficacy of this strategy is limited to mitigating shuttle effects within an excessive electrolyte environment. This limitation arises because reduced electrolyte levels substantially elevate the concentrations of long-chain and short-chain LiPSs, which can chemically or electrochemically react with the Li 2 S end product, thereby exacerbating parasitic reactions at the Li anode. Furthermore, the conventional catalysts loaded onto carbon surfaces predominantly exist in nano-/submicron-scale sizes, rendering them susceptible to dissolution or aggregation and leading to a diminished utilization of catalytic sites. Hence, there is an urgent need to identify an efficient catalyst suitable for electrolyte-deficient LSBs. After millions of years of evolution, nature have evolved a series of exquisite and efficient catalytic systems, which provides a good reference for the design of catalytic materials. Cytochrome c oxidase (CcO), consisting of stereo-conformation structure with an inner iron-based heme active center and outer organic ligand layer, is a key component on the inner mitochondrial membrane respiratory chain due to its high oxygen reduction activity 20 – 22 . The proton-pumping activity of CcO facilitates the movement of H + ions across the mitochondrial membrane, establishing a crucial proton gradient for ATP synthesis 23 . Additionally, the Cu(I) site at the enzyme edge plays a pivotal role in electron transfer to the heme iron atom and the internal Cu(II) site. This results in redox reactions at the Fe/Cu(II) bimetallic center, where coordinated -OH groups are protonated to produce water molecules, creating a cavity between the Fe and Cu(II) sites that enhances the catalysis of subsequent oxidation reactions 24 . In our previous work, we inspired by the high-efficient biological enzyme catalysis system and proposed a periodic expansion catalysis theory which bridge the gap between oxidation catalysis to sulfur catalysis 25 . Based on this guidance, simulating the high-efficient CcO and harnessing the multifunctional Cu active sites and Fe catalytic centers may guide novel biomimetic catalysts design for high-performance LSB systems. As for LSBs, the biomimetic catalyst should adjust the structure and composition of natural enzymes to adapt to organic solvent environment and strong electric field environment. Similar to natural enzymes, biomimetic catalysts possess highly dispersed single-atom active sites, stable spatial configurations, and variable local environments, showing a great potential in catalytic conversion of LiPSs. However, in fact, we found that most of these biomimetic enzymes would be dissolved in organic solvents and thus caused active center lost 26 . A good solution is to immobilize them on conductive substrates, such as functionalized carbon nanotubes, graphene, or metal nanowires, which can achieve rapid electron transfer capability. Another important challenge is that the catalytic centers of biomimetic enzymes are easily inactivated by the influence of electrolyte and electric field. Building shells on the biomimetic enzymes may be a good choice to ensure long-term stability and activity, as demonstrated by the encapsulation of metal-organic-frameworks (MOF) 27 , covalent-organic-frameworks (COF) 28 , 29 , and molecular sieves in recent reports 30 . In this study, we developed a biomimetic catalyst of Fe-TCPP@Cu-BTC to mimic the multifunctional Cu active site and iron-based heme catalytic center of CcO (Scheme 1 ). The catalyst was constructed by encapsulating iron tetrakis(carboxyphenyl)-porphyrin (Fe-TCPP) in copper benzene-1, 3, 5-tricarboxylate (Cu-BTC) MOF, as illustrated in Fig. 1 a, to improve its adaptability and stability in lithium-sulfur chemistry. Through a series of theoretical simulations and experimental tests, we found that Cu-BTC can aggregate a large amount of LiPSs by leveraging its high surface area and strong adsorption capabilities. The Cu atoms within Cu-BTC form bimetallic centers with Fe atoms in Fe-TCPP, promoting the homolytic cleavage of Li 2 S n species to into LiS n/2 and accelerating their conversion to Li 2 S. Furthermore, enzyme-like properties were observed in Fe-TCPP@Cu-BTC, which could significantly reduce the activation energy of sulfur conversion rate. The assembled coin LSB exhibited an initial capacity of 1296 mAh g − 1 and maintained 885 mAh g − 1 after 100 cycles at a sulfur loading of 5.6 mg cm − 2 and an E/S ratio of 6.5 µL mg − 1 . To further verify its practicality, the pouch cell was assembled with a sulfur loading of 4.0 mg cm − 2 and an E/S ratio of 4 µL mg − 1 . It retained a capacity of 986 mAh g − 1 after 50 cycles, corresponding to an energy density exceeding 300 Wh kg − 1 . 2. Results and Discussions Figure 1 a illustrates the schematic synthesis procedure of Fe-TCPP@Cu-BTC and Cu-BTC by a conventional hydrothermal method 31 . The Fe-TCPP@Cu-BTC exhibits regular octahedral crystals, whose morphology is similar to Cu-BTC (Supplementary Fig. 1). Element mappings reveals uniform distribution of Cu and Fe atoms in Fe-TCPP@Cu-BTC, suggesting even dispersion of Fe-TCPP molecules within Cu-BTC channels (Supplementary Fig. 2). The powder X-ray diffraction (PXRD) reveals no obvious peak shifts from Cu-BTC to Fe-TCPP@Cu-BTC (Fig. 1 b), reconfirming the encapsulation of Fe-TCPP in Cu-BTC frameworks. Based on these findings, Supplementary Fig. 3 provided the optimized Fe-TCPP@Cu-BTC molecular model according to the first principle simulations. Furthermore, Fourier-transform infrared (FT-IR) and UV-vis absorption spectroscopy were used to investigate the chemical interactions between Fe-TCPP and Cu-BTC. As depicted in Fig. 1 c, the featured C-H bonding vibration peak of pyrrole (~ 1001 cm − 1 ) in Fe-TCPP experienced a higher wavenumber (1003 cm − 1 ) shift upon combination Cu-BTC (Fe-TCPP@Cu-BTC) 31 , 32 . This FT-IR finding implies the occurrence of chemical bonding between Fe-TCPP and Cu-BTC. UV-vis absorption spectra in Fig. 1 d revealed a noticeable shift in the intense Soret band (~ 420 nm) compared to Fe-TCPP (~ 416 nm), likely due to depolymerization induced by Cu-BTC and subsequently self-assembly between Fe-TCPP and Cu-BTC 33 . Consequently, nitrogen adsorption-desorption tests yielded a specific surface area of 695.0 m 2 g − 1 for Fe-TCPP@Cu-BTC, slightly lower than the 907.4 m 2 g − 1 of Cu-BTC (Supplementary Fig. 4). In addition, X-ray photoelectron spectroscopy (XPS) was employed to evaluate the impact of Fe-TCPP on the electronic structure of Cu-BTC. Compared to Cu-BTC, the binding energies of Fe-TCPP@Cu-BTC for Cu 2p core levels were up-shifted from 952.2/932.5 to 954.1/934.4 eV and the O 1s core level shifted from 531.5 to 532.3 eV (Fig. 1 f and Supplementary Fig. 5b) 34 , 35 . On the contrary, the binding energies of Fe 2p core level were down-shifted from 724.8/711.5 to 722.4/710.1 eV, and the N 1s core level shifted from 399.9/397.7 to 400.6/398.8 eV (Fig. 1 g and Supplementary Fig. 5a) 36 , 37 . This means the existence of electron transfer from outer Cu-BTC to inner Fe-TCPP in Fe-TCPP@Cu-BTC, which can chemically anchor Fe-TCPP and thereby inhibit its dissolution. Supplementary Fig. 6 illustrates the stability of Fe-TCPP@Cu-BTC and Fe-TCPP in a standard LSB electrolyte. It demonstrates that the encapsulation of Fe-TCPP with Cu-BTC effectively prevents Fe-TCPP dissolution. The local solvent environment on the catalyst surface was probed using FT-IR spectroscopy (Fig. 1 e), where Fe-TCPP@Cu-BTC was immersed in DME for 2 h followed by drying. In this scenario, the peaks at 1110 and 940 cm ‒ 1 correspond to the C‒O and O‒Cu bonds of Cu-BTC 31 ; while the peak at 2878 cm ‒ 1 corresponds to the ‒CH 3 group of DME 38 . Upon treatment with DME, the characteristic C‒O and O‒Cu signals of Fe-TCPP@Cu-BTC shifted to 1090 and 917 cm ‒ 1 , respectively; while the ‒CH 3 signal of DME shifted to 2931 cm ‒ 1 . This observation likely originates from dipole-dipole interactions between the solvent and Cu-BTC. As previously reports, these interactions between the catalyst and solvent may facilitate the desolvation of LiPSs, thereby promoting their smooth conversion 36 . To elucidate the behavior of LiPSs within Fe-TCPP@Cu-BTC and to further substantiate our hypothesis, density functional theory (DFT) simulations were conducted to mimic the sequential sulfur transformations throughout the adsorption-catalysis-desorption processes, as illustrated in Fig. 2 . The existence of abundant oxygen-containing functional groups within the Cu-BTC component of the Fe-TCPP@Cu-BTC catalyst facilitates the formation of Li‒O bonds with Li in LiPSs during the reduction process, which in turn attract LiPSs to congregate around the Fe-TCPP@Cu-BTC. Under the influence of an electric field, the Cu-BTC component catalyzes the transformation of Li 2 S 8 into shorter-chain Li 2 S 6 , and their shrunk lengths and reduced volumes enable them to penetrate more readily the cavities of the Fe-TCPP@Cu-BTC 39 . Upon entering the cave formed by Fe-TCPP@Cu-BTC, the terminal S (S T ) atoms of Li 2 S 6 interact with the Cu and Fe components of the Fe-TCPP@Cu-BTC, leading to the formation of Cu-S and Fe-S bonds. Note that this interaction is significantly exothermic by 27.0 kcal/mol, indicating that the encapsulation of Li 2 S 6 in this cavity is thermodynamically favorable and likely to occur spontaneously. The subsequent cleavage of Li 2 S 6 , facilitated by the strain exerted on the sulfur skeleton by the Cu-S and Fe-S bonds (as evidenced by the difference in S-S bond lengths in state I and pristine Li 2 S 6 ), may occur through three distinct pathways, denoted as II a , II b , and II c , culminating in the formation of Li-S x -M (where x = 2, 3, or 4) moieties, respectively. Obviously, the homolytic cleavage leading to the formation of Li-S 3 -M in II b is thermodynamically favored over the heterolytic cleavage into Li-S x -M (x = 2 or 4) (-9.1 kcal/mol vs. -1.2 and 11.0 kcal/mol, respectively, relative to state I), which aligns well with experimental observations and previous reports. Continuing with a constant supply of Li + in the environment, the S 3 moiety within Li-S 3 -M tends to further divide into S y and S 3 − y -M (where y = 1 or 2), generating dissociative Li 2 S or Li 2 S 2 species. The production of Li 2 S/LiS 2 -M in IV a and Li 2 S z /LiS 3 − z -M (where z = 1 or 2) in IV b involves energetically more demanding steps by 61.0 and 27.2 kcal/mol, as compared to the less energy-intensive formation of Li 2 S 2 /LiS-M in IV c and Li 2 S z /LiS 3 − z -M (where z = 1 or 2) in IV d by 16.7 and 17.2 kcal/mol, respectively, with reference to the Li-S 3 -M state denoted as III in this progression. The final cleavage of the remaining S-M bonds in V c , facilitated by additional Li + , can proceed smoothly through a slightly endothermic step of 7.2 kcal/mol, completing the sulfur reduction process. Conversely, the transformation from IV d is thermodynamically quite disfavored. Therefore, the sulfur transformation process is envisioned to proceed in a stepwise manner through stages I – II b – III – IV c – V c – VI c , as illustrated in Fig. 2 . The interactions between Fe-TCPP@Cu-BTC and LiPSs were further investigated through static adsorption tests. As depicted in Supplementary Fig. 7 , the fading of the yellow Li 2 S 6 solution after 12 h of treatment with Fe-TCPP@Cu-BTC, Cu-BTC, Fe-TCPP, and CNTs followed a color depth order of Li 2 S 6 > CNTs > Fe-TCPP > Cu-BTC > Fe-TCPP@Cu-BTC, indicating the highest LiPS absorptivity of Fe-TCPP@Cu-BTC 40 . Subsequently, XPS measurements were conducted to analyze the compositions of the soaked Fe-TCPP@Cu-BTC, Cu-BTC, Fe-TCPP, or CNTs surfaces. As shown in Figs. 3 a ‒c , distinct Cu 2p and Fe 2p XPS peaks were observed in Li 2 S 6 -treated Fe-TCPP@Cu-BTC (Cu 2p: ~950.8/930.8 eV; Fe 2p: 723.9/710.0 eV), Li 2 S 6 -treated Cu-BTC (Cu 2p: ~953.0/933.1 eV), and Li 2 S 6 -treated Fe-TCPP (Fe 2p: ~724.5/710.9 eV), corresponding to Cu‒S and Fe‒S bond formations resulting from Cu atoms of Cu-BTC, Fe atoms of Fe-TCPP, and S atoms of LiPSs 41 – 43 . This observation was corroborated by the S 2p XPS spectra and corresponding deconvolution analysis (Fig. 3 c). The presence of Fe and Cu atoms led to shifts in the binding energies of bridge S (S B ) and S T in Li 2 S 6 -treated Fe-TCPP@Cu-BTC towards higher fields, confirming the formation of Fe‒S and Cu‒S bonds. Moreover, compared to Li 2 S 6 -treated CNTs, the higher binding energy shifts of S B and S T in Li 2 S 6 -treated Fe-TCPP@Cu-BTC, Cu-BTC, and Fe-TCPP indicated decreased electron density, suggesting the catalyst's mediation of sulfur conversions. Additionally, a lower binding energy shift of Li 1s XPS peaks was observed in Li 2 S 6 -treated Fe-TCPP@Cu-BTC compared to Li 2 S 6 -treated Cu-BTC, Li 2 S 6 -treated Fe-TCPP, and Li 2 S 6 -treated CNTs (Supplementary Fig. 8). Consequently, the O 1s and N 1s peaks shifted towards higher binding energy after Li 2 S 6 treatment, indicating strong electron transfer from O and N atoms of Fe-TCPP@Cu-BTC to Li atoms of Li 2 S 6 , leading to Li···O and Li···N bond formation, known as Li-bonds, according to previous reports (Supplementary Fig. 9) 36 . These interactions, mainly through Li-bonds and Fe‒S/Cu‒S bonds, resulted in LiPS enrichment in Fe-TCPP@Cu-BTC and inhibited the shuttle effect of LiPSs. The catalytic effect of Fe-TCPP@Cu-BTC on LiPSs was extensively investigated through cyclic voltammetry (CV) tests in a symmetrical battery employing Li 2 S 6 electrolyte (Supplementary Fig. 10). Fe-TCPP@Cu-BTC cells exhibited a significantly higher current density compared to Cu-BTC, Fe-TCPP, and CNTs, indicative of substantially improved redox kinetics of LiPSs by Fe-TCPP@Cu-BTC. Electrochemical reactivity was further assessed via CV analysis. Supplementary Fig. 11a‒d illustrates the initial CV profiles of cells with Fe-TCPP@Cu-BTC, Cu-BTC, Fe-TCPP, and CNTs at a rate of 0.1 mV s ‒ 1 , revealing two major peaks at ~ 2.31 and 2.05 V, corresponding to the reduction of S 8 to soluble long-chain LiPS (Li 2 S n , 4 ≤ n ≤ 8), and further to solid Li 2 S 2 /Li 2 S, respectively. The oxidation peaks at ~ 2.42 V are attributed to the conversion from Li 2 S 2 /Li 2 S to Li 2 S n and S 8 . Comparing with other control cells, the CV curve of the Fe-TCPP@Cu-BTC cell displays a distinct positive shift of the cathodic peak and negative shift of the anodic peak (Supplementary Fig. 12a‒b), indicating reduced voltage polarization and enhanced reaction kinetics influenced by Fe-TCPP@Cu-BTC. Furthermore, sulfur redox kinetics were quantitatively evaluated using Tafel slopes based on each individual process (Fig. 3 a‒b and Supplementary Fig. 13). The Fe-TCPP@Cu-BTC cell also demonstrated the smallest value of 28.3, 33.4, and 43.7 mV dec ‒ 1 at S 8 →Li 2 S n , Li 2 S n →Li 2 S, and Li 2 S→Li 2 S n conversions, respectively, compared to Cu-BTC (32.3, 52.6, and 85.1 mV dec ‒ 1 ), Fe-TCPP (38.4, 62.3, and 111.7 mV dec ‒ 1 ), and CNTs (41.9, 70.9, and 132.7 mV dec ‒ 1 ). These results highlight the excellent redox reaction kinetics behaviors and electrochemical reversibility of Fe-TCPP@Cu-BTC. Additionally, the Li + diffusion coefficient in each cathode was quantified using CV tests under various scan rates ranging from 0.10 to 0.30 mV s − 1 . Plots in Fig. 3 d, Supplementary Fig. 14, and Supplementary Fig. 15a‒c indicate that the peaks for cells with Fe-TCPP@Cu-BTC are much more intense than those for the other three cells, suggesting promoted LiPS conversions by Fe-TCPP@Cu-BTC. The Li ion diffusion properties were estimated using the classical Randles-Sevcik equation. The cells with Fe-TCPP@Cu-BTC exhibited larger slopes of lithium-ion diffusion coefficient (P A = 3.24 × 10 ‒9 ; P B = 1.30 × 10 ‒8 ; P C = 2.65 × 10 ‒8 cm 2 s ‒ 1 ) compared to Cu-BTC (2.95 × 10 ‒9 ; 6.39 × 10 ‒9 ; 1.83 × 10 ‒8 cm 2 s ‒ 1 ), Fe-TCPP (2.06 × 10 ‒9 ; 5.97 × 10 ‒9 ; 1.51 × 10 ‒8 cm 2 s ‒ 1 ), and CNTs (1.40 × 10 ‒9 ; 5.52 × 10 ‒9 ; 7.94 × 10 ‒9 cm 2 s ‒ 1 ), demonstrating enhanced LiPS conversion kinetics of Fe-TCPP@Cu-BTC throughout the charge/discharge processes. Nucleation Transformation Ratio (NTR) was used to assess the kinetics behaviors of the cathode reactions 44 . All NTR values for Fe-TCPP@Cu-BTC cells at different scan rates were close to 3, indicating rapid transformation of LiPSs to Li 2 S facilitated by Fe-TCPP@Cu-BTC (Fig. 3 g). The process of converting LiPSs to Li 2 S during discharge accounts for three-quarters of the theoretical capacity, underscoring the importance of enhancing kinetics in this phase. To investigate the impact of Fe-TCPP@Cu-BTC on this conversion, we conducted potentiostatic intermittent titration technique (PITT) tests on cells, focusing on liquid–solid conversion kinetics (see Supplementary Fig. 16). Generally, PITT discharge curves exhibit two distinct regions: the first involves liquid-liquid conversion from long-chain to short-chain LiPS, while the second region entails liquid-solid conversion, corresponding to Li 2 S deposition. In the initial process, the addition of Fe-TCPP@Cu-BTC led to notable enhancements in initial current responses, with increases of 55% (Cu-BTC), 134% (Fe-TCPP), and 228% (CNTs) at each potentiostatic step, indicating improved liquid-liquid conversion kinetics. Subsequently, during the second process, the Li 2 S deposition peak time was earliest for the Fe-TCPP@Cu-BTC cell (1970 s), indicative of a faster deposition rate 45 – 47 . Further Li 2 S nucleation tests were conducted, with results detailed in Supplementary Fig. 16. According to Faraday’s law, deposition capacities on Fe-TCPP@Cu-BTC, Cu-BTC, Fe-TCPP, and CNTs electrodes were measured at 236.9, 182.9, 175.7, and 142.6 mAh g − 1 , respectively 48 . These findings highlight the ability of Fe-TCPP@Cu-BTC to inhibit shuttle effects and enhance sulfur utilization, thereby enabling high-capacity Li 2 S precipitations. Dynamic monitoring techniques were employed to trace the sulfur evolution features. In-situ ultraviolet‒visible (UV‒Vis) absorption spectra of four cells: Fe-TCPP@Cu-BTC, Cu-BTC, Fe-TCPP, and CNTs are depicted in Supplementary Fig. 18‒19. Each cell exhibits characteristic absorption peaks at approximately 492, 475, 420, and 617 nm, corresponding to S 8 2− , S 6 2− , S 4 2− , and S 3 2− /S 3 *− anions, respectively. During discharge, the Fe-TCPP@Cu-BTC cell demonstrated the most rapid decrease in S 8 2− intensity compared to other cells in the Li 2 S 8 electrolyte (Fig. 4 a) 40 . Moreover, the intensity of S 3 2‒ /S 3 * ‒ initially increased followed by a decrease, indicating its role as an intermediate bridge for Li 2 S 2 /Li 2 S formation. A similar trend was observed in the Li 2 S 4 electrolyte (Fig. 4 b), suggesting the capability of Fe-TCPP@Cu-BTC catalyst to promote both long-chain and short-chain LiPS conversion, along with Li 2 S 2 /Li 2 S generation. Notably, unlike other samples, the Fe-TCPP sample exhibited an additional absorption peak at 430 nm, which is the characteristic of porphyrin iron, further confirming Fe-TCPP's tendency to dissolve in the electrolyte. To gain a deeper insight into the catalytic effect of Fe-TCPP@Cu-BTC on sulfur species transformation, in-situ Raman spectra were measured (Figs. 4 c‒f, Supplementary Fig. 20). Without a catalyst (Fig. 4 f, Supplementary Fig. 20d), only the S 8 /Li 2 S 8 peak (152, 246, 437, 472 cm ‒ 1 ) was observed, persisting even after discharge to 1.6 V, indicating incomplete sulfur reduction, which leads to the poor CNT cell performance. However, with Fe-TCPP@Cu-BTC, the intensity of the S 8 /Li 2 S 8 peak gradually decreased during discharge. By 2.5 V discharge, peaks of S 6 2‒ (325 cm ‒ 1 ) and S 4 2‒ (496 cm ‒ 1 ) emerged, while the S 8 /Li 2 S 8 peak vanished, indicating decomposition into Li 2 S 6 and Li 2 S 4 . When discharging to 2.0 V, Li 2 S 6 vanished, replaced by a Li 2 S 4 peak (496 cm ‒ 1 ), along with a small amount of S 3 2‒ /S 3 *‒ (534 cm ‒ 1 ) and Li 2 S 2 (510 cm ‒ 1 ). Upon discharge to 1.6 V, Li 2 S 4 and S 3 2‒ /S 3 *‒ were consumed, yielding Li 2 S 2 and Li 2 S (375 cm ‒ 1 ), indicating complete conversion of S 8 /Li 2 S 8 to Li 2 S 2 /Li 2 S 49–51 . The Cu-BTC cell (Fig. 4 d, Supplementary Fig. 20b) exhibited slower disappearance or generation of sulfur species compared to the Fe-TCPP@Cu-BTC cell. Notably, the S 8 /Li 2 S 8 peak vanished at 2.3 V, while complete consumption and generation of S 8 /Li 2 S 6 , Li 2 S 3 /Li 2 S 4 occurred at 2.4 V, 2.1 V, 1.8 V, and 1.9 V, respectively, along with a small production of Li 2 S 2 . Moreover, the solubility of Fe-TCPP in the electrolyte could cause catalyst loss, reducing sulfur reaction kinetics. In the Fe-TCPP cell (Fig. 4 e, Supplementary Fig. 20c), only the disappearance of S 8 /Li 2 S 8 (2.1 V) and generation of Li 2 S 6 were detected. Thus, the addition of Fe-TCPP@Cu-BTC catalyst facilitated sulfur species reduction via homolysis, increasing the sulfur reduction pathways and ensuring rapid and complete sulfur conversion. The semi-in-situ analysis of Cu 2p and Fe 2p XPS spectra further elucidated the catalytic mechanisms, as depicted in Figs. 4 g‒h. Evidently, the Cu 2p 1/2 , Cu 2p 3/2 , and Cu‒S peaks associated with Cu-BTC for the Fe-TCPP@Cu-BTC cell gradually shifted to lower binding energies (Cu 2p 1/2 /Cu 2p 3/2 and Cu‒S; 2.8 V: 954.1/933.5 eV and 952.0/932.0 eV; 2.1 V: 953.4/933.1 eV and 951.6/931.8 eV; 1.6 V: 953.7/932.6 eV and 951.3/930.7 eV, respectively) compared to the Cu-BTC cell (Cu 2p 1/2 /Cu 2p 3/2 and Cu‒S; 2.8 V: 954.4/934.4 eV and 952.8/933.7 eV; 2.1 V: 954.3/934.4 eV and 952.8/933.3 eV; 1.6 V: 953.9/933.9 eV and 952.6/933.0 eV, Supplementary Fig. 21a). Similar observations were made for the Fe 2p 1/2 , Fe 2p 3/2 , and Fe‒S peaks in Fe-TCPP@Cu-BTC (Fe 2p 1/2 / Fe 2p 3/2 and Fe‒S; 2.8 V: 727.7/714.0 eV and 725.7/712.1 eV; 2.1 V: 727.4/713.9 eV and 724.3/711.4 eV; 1.6 V: 727.0/712.9 eV and 724.0/710.8 eV, respectively) and Fe-TCPP cell (Fe 2p 1/2 / Fe 2p 3/2 and Fe‒S; 2.8 V: 728.3/714.3 eV and 726.7/712.3 eV; 2.1 V: 728.1/714.3 eV and 725.9/712.0 eV; 1.6 V: 727.9/714.3 eV and 725.8/711.9 eV, Supplementary Fig. 21b) 52 , 53 . The lower binding energy shifts of Fe‒S and Cu‒S bonds during the discharge process suggest enhanced interactions between Cu and S, and Fe and S atoms, facilitating the breakage of S‒S bonds from long-chain to short-chain LiPSs. Moreover, the Cu‒S and Fe‒S bonds between LiPSs and Fe-TCPP@Cu-BTC led to a gradual increase in the electron cloud density around Cu and Fe atoms, which contributing to S‒S bond breaking. To reveal the enzymatic catalysis mechanism of Fe-TCPP@Cu-BTC, a steady-state kinetic analysis was conducted by varying the concentration of S 3 *‒ within a fixed concentration of Fe-TCPP@Cu-BTC by in-situ UV‒Vis spectra, which exhibited conformity with the classic Michaelis‒Menten kinetics throughout all stages of discharge processes (Figs. 5 c‒d). The Michaelis‒Menten plots provided values for the enzyme kinetic parameters of Michaelis‒Menten constants ( K m ), where K m reflects the affinity of the biomimetic enzyme towards the substrate (lower K m indicates a higher affinity) and V max indicates the catalytic activity of the biomimetic enzyme. Compared to Cu-BTC (fitting the equation within 2.5–2.2 V with K m = 1.02×10 − 3 mM) and Fe-TCPP (fitting the equation within 2.1–1.6 V with K m = 3.89×10 − 2 mM), Fe-TCPP@Cu-BTC exhibits consistently smaller K m values throughout the entire sulfur conversion range (2.8–2.2 V, K m = 5.92×10 − 3 mM; 2.1–1.6 V, K m = 7.79×10 − 4 mM) (see Supplementary Table 1). In contrast, CNTs did not exhibit conformity with this kinetics (Supplementary Fig. 22). These findings indicate that the Fe-TCPP@Cu-BTC biomimetic enzyme exhibits higher affinity, which is consistent with LiPS adsorption findings (see Supplementary Fig. 7). Furthermore, V max was determined at different sulfur conversion segments. The Fe-TCPP@Cu-BTC (2.8–2.2 V: V max = 5.87×10 − 4 mM min − 1 ; 2.1–1.6 V: V max = 1.87×10 − 4 mM min − 1 ) is about two orders of magnitude higher than that of Fe-TCPP (2.5–2.2 V: V max = 8.47×10 − 6 mM min − 1 ) and Cu-BTC (2.1–1.6 V: V max = 1.24×10 − 6 mM min − 1 ) (see Supplementary Table 2). This suggests that the homolytic reaction of LiPSs under the influence of this biomimetic enzyme can increase the sulfur conversion rate by nearly 100 times. To disclose the kinetic improvements in sulfur redox reactions, the activation barrier at specific voltages was experimentally determined. This was achieved by fitting the charge transfer resistance measured at various temperatures using electrochemical impedance spectroscopy (EIS), to the activation energy ( E a ) (Fig. 5 e and Supplementary Fig. 23–28). The Fe-TCPP@Cu-BTC cell exhibited a significantly lower E a value (0.29–1.03 eV) compared to Cu-BTC (0.34–1.20 eV), Fe-TCPP (0.38–1.25 eV), and CNTs (0.55–1.42 eV) cells within the voltage range of 2.4–1.6 V. These results demonstrate that Fe-TCPP@Cu-BTC can catalyze the conversion of both long-chain and short-chain LiPSs more effectively 54 . The rate performance demonstrates that the Fe-TCPP@Cu-BTC cell delivers superior discharge capacities of 1522, 1162, 1079, 1024, and 970 mAh g − 1 at 0.2, 0.5, 1.0, 1.5, and 2.0 C, respectively (Fig. 6 a). When the rate returns to 1.5, 1.0, 0.5, and 0.2 C, the reversible capacities are restored to 1000, 1023, 1054, and 1189 mAh g − 1 , respectively. In contrast, the control cells exhibit significant fluctuation and a general attenuation trend with changing rates. The improved performance of the Fe-TCPP@Cu-BTC cell indicates a kinetically efficient reaction process with fast electron transfer. Additionally, the galvanostatic charge-discharge curves of the Fe-TCPP@Cu-BTC electrode at various C-rates (0.2–2.0 C) are shown in Fig. 6 b, revealing that the polarization of the charge-discharge curves increases slightly with higher C-rates. The decreased overpotential, superior rate capability, and high reversibility of the Fe-TCPP@Cu-BTC cell result from improved electrochemical kinetics, as further revealed by electrochemical impedance spectroscopy (EIS). Supplementary Fig. 29 illustrates the impedance for both control and Fe-TCPP@Cu-BTC cells after 0, 3, and 10 cycles. After 10 cycles, the R e (resistance of electrolyte), R ct (resistance of charge transfer), and R mt (resistance of mass transfer) of the Fe-TCPP@Cu-BTC cell remain similar to those at 3 cycles, indicating continuous cycling stability of electrons/ions and improved sulfur utilization. It is reasonable to speculate that a solid electrolyte interphase (SEI) film forms after three cycles in the Fe-TCPP@Cu-BTC cell. Detailed impedance data is provided in Supplementary Tables 1‒4. Moreover, the Fe-TCPP@Cu-BTC catalyst exhibits excellent long-term cycling performance for the Li–S cell. Figure 6 c and Supplementary Fig. 30 shows that the Fe-TCPP@Cu-BTC cell delivers a high initial discharge capacity of 1548 mAh g − 1 at 0.2 C, maintaining 935 mAh g − 1 after 150 cycles. In contrast, the control cells (Cu-BTC, Fe-TCPP, and CNTs) deliver initial capacities of 1406, 1395, and 1298 mAh g − 1 , maintaining 733, 574, and 448 mAh g − 1 after 150 cycles, respectively. The cycling stability of these cells was further measured at 1.0 C. Compared with Cu-BTC (0.056%), Fe-TCPP (0.075%), and CNTs (0.111%), the Fe-TCPP@Cu-BTC cell shows the highest capacity retention (Fig. 6 d, Supplementary Fig. 31) and the lowest capacity decay (0.043% per cycle) with an initial discharge capacity of over 1016 mAh g − 1 and maintaining 751 mAh g − 1 after 600 cycles. Furthermore, higher sulfur loadings of 4.5, 5.6, and 6.2 mg cm − 2 were tested under an electrolyte/sulfur (E/S) ratio of 6.5 µL mg − 1 , with initial discharge capacities of 1350, 1296, and 1280 mAh g − 1 , fading to 976, 885, and 682 mAh g − 1 after 100 cycles (Fig. 6 e). The superior stabilization effect of Fe-TCPP@Cu-BTC is confirmed by the pouch cell (Fig. 6 f), which exhibited a high initial discharge capacity of 5.2 mAh cm − 2 (1435 mAh g − 1 ) with a sulfur loading of 4.0 mg cm − 2 and an E/S ratio controlled at 4 µL mg − 1 . After 50 cycles, the capacity still maintains above 3.7 mAh cm − 2 (986 mAh g − 1 ). The pouch cell performance parameters for the first discharge cycle are summarized in Fig. 6 g, showing a high specific discharge capacity of 1299 mA h g − 1 , providing a total discharge capacity of 0.104 Ah. The average voltage was 2.19 V, and the discharge energy of the pouch cell was 0.228 Wh. Based on the total mass, the actual energy density of the pouch cell was calculated to be 300.4 Wh kg − 1 . 3. Conclusion In this study, we developed a biomimetic catalyst, Fe-TCPP@Cu-BTC, to emulate the multifunctional Cu active site and the iron-based heme catalytic center of cytochrome c oxidase. Through a series of theoretical simulations and experimental analyses, we found that Cu-BTC can aggregate a large amount of LiPSs due to its high surface area and strong adsorption capabilities. The Cu-Fe bimetallic center within the spatially confined Fe-TCPP@Cu-BTC significantly promotes the homolytic cleavage of Li 2 S 6 to LiS 3 and accelerates their subsequent conversion to Li 2 S. The enzyme-like properties were further evaluated using Michaelis-Menten kinetics, confirming that the homolytic reaction can increase the sulfur conversion rate by nearly 100-fold. As a result, the Fe-TCPP@Cu-BTC-based coin-type LSB with a sulfur loading of 5.6 mg cm⁻² and an E/S ratio of 6.5 µL mg⁻¹ exhibited an initial capacity of 1296 mAh g⁻¹ at 0.1 C and maintained 885 mAh g⁻¹ after 100 cycles. To further verify its practicality, a pouch cell was assembled with a sulfur loading of 4.0 mg cm⁻² and an E/S ratio of 4 µL mg⁻¹. It retained a capacity of 986 mAh g⁻¹ after 50 cycles, corresponding to an energy density exceeding 300 Wh kg⁻¹. This work opens up new possibilities for catalyst design in energy storage systems, potentially leading to breakthroughs in other areas of electrochemistry and materials science. It underscores the value of drawing inspiration from nature’s efficient catalytic systems to solve complex technological challenges. Declarations Supporting Information Supporting Information is available from the Wiley Online Library or from the author. Acknowledgements This research was funded in part by Natural Science Foundation of Zhejiang Province (Grant No. LQ22B030003 and LY22B030002), National Natural Science Foundation of China (Grant Nos. 22309136, 22109119, 51972238), Major Scientific and Technological Innovation Project of Wenzhou City (Grant No. ZG2021013) and Xinmiao Foundation of Zhejiang Province (Grant No. 2024R429B042). Conflicts of Interest There are no conflicts to declare. Data Availability Statement Research data are not shared. Author Contributions T.L., Y. Dong and Z.G. contributed equally to this work. T. L. performed all the experiments with the assistance of M.S., S.Y., M.Z. and H.N., J.G. and H.T.. D.C.analyzed the data and prepared the results. Z.G., J.G. and H.T. conducted the MD simulations and the theoretical calculations. D.C. and H.T. planned the study and composed the manuscript. Z.Y. conceived and supervised the project. 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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-4727879","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":328483226,"identity":"e1dc420a-9a48-4149-a545-5a07115eaf2a","order_by":0,"name":"Dong 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04:30:27","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4727879/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4727879/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":60668532,"identity":"b1a0e2e2-ceba-443d-9579-baeb63787b93","added_by":"auto","created_at":"2024-07-19 09:47:36","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":149615,"visible":true,"origin":"","legend":"\u003cp\u003ea) Schematic illustration of synthesizing Fe-TCPP@Cu-BTC biomimetic enzymes. b) XRD spectra of Cu-BTC and Fe-TCPP@Cu-BTC. c) FT-IR of Fe-TCPP, Fe-TCPP@Cu-BTC, and Cu-BTC. d) UV-vis absorption spectroscopies of Fe-TCPP, Fe-TCPP, Cu-BTC mixed physically (Fe-TCPP+Cu-BTC), and Fe-TCPP@Cu-BTC. e) FT‒IR spectra of DME, Fe-TCPP@Cu-BTC, and Fe-TCPP@Cu-BTC with DME. f) Cu 2p, g) Fe 2p XPS sepctra of Fe-TCPP and Fe-TCPP@Cu-BTC.\u003c/p\u003e","description":"","filename":"image2.png","url":"https://assets-eu.researchsquare.com/files/rs-4727879/v1/94b3cddae36483e46b5100a2.png"},{"id":60668551,"identity":"a12e7f30-55d7-458e-a1e5-144477758828","added_by":"auto","created_at":"2024-07-19 09:47:36","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":928543,"visible":true,"origin":"","legend":"\u003cp\u003eScheme of DFT theoretical calculation for Fe-TCPP@Cu-BTC catalytic mechanisms in sulfur conversion includes three main steps. Step I and II involve comparing the dissociation processes of Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e and LiS\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e-\u003c/sup\u003e. Step III focuses on the desorption of Li\u003csub\u003e2\u003c/sub\u003eS.\u003c/p\u003e","description":"","filename":"image3.png","url":"https://assets-eu.researchsquare.com/files/rs-4727879/v1/bb1e405b6d807058d65441ee.png"},{"id":60669428,"identity":"ed9166fa-2f2d-4968-b22f-5eebaac284b7","added_by":"auto","created_at":"2024-07-19 09:55:36","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":103667,"visible":true,"origin":"","legend":"\u003cp\u003eChemical interactions between Fe-TCPP@Cu-BTC and LiPSs. a) Cu 2p core levels of Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e treated Fe-TCPP@Cu-BTC and Cu-BTC; b) Fe 2p core levels of Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e treated Fe-TCPP@Cu-BTC and Fe-TCPP; c) S 2p XPS spectra of Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e treated Fe-TCPP@Cu-BTC, Cu-BTC, Fe-TCPP and CNTs; d-e) Tafel plots corresponding to the reductions of S\u003csub\u003e8\u003c/sub\u003e to Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003en\u003c/sub\u003e and Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003en\u003c/sub\u003e to Li\u003csub\u003e2\u003c/sub\u003eS; f) Linear fits of the peak current of Fe-TCPP@Cu-BTC cathode at different scan rates. g) NTR values of Fe-TCPP@Cu-BTC, Cu-BTC, Fe-TCPP, and CNTs cathodes at different sweep rates.\u003c/p\u003e","description":"","filename":"image4.png","url":"https://assets-eu.researchsquare.com/files/rs-4727879/v1/b4b0774fc0c725b821076243.png"},{"id":60669429,"identity":"1d512010-8765-40e8-8c29-663b5bc8936c","added_by":"auto","created_at":"2024-07-19 09:55:36","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":204480,"visible":true,"origin":"","legend":"\u003cp\u003eDynamic sulfur conversion recorded by \u003cem\u003ein/ex\u003c/em\u003e situ spectroscopies. The normalized absorbance of a) S\u003csub\u003e8\u003c/sub\u003e\u003csup\u003e2-\u003c/sup\u003e (492 nm) and S\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e2−\u003c/sup\u003e/S\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e*−\u003c/sup\u003e (617 nm) in Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e8\u003c/sub\u003e solution, b) S\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2- \u003c/sup\u003e(475 nm) and S\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e2−\u003c/sup\u003e/S\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e*− \u003c/sup\u003e(617 nm) in Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e4\u003c/sub\u003e as a function of potential at\u0026nbsp; electrodes surfaces with different catalysts. \u003cem\u003eIn situ\u003c/em\u003e Raman spectra of the electrode with c) Fe-TCPP@Cu-BTC, d) Cu-BTC, e) Fe-TCPP, and f) CNTs. \u003cem\u003eEx situ\u003c/em\u003e XPS of g) Fe 2p and h) Cu 2p core levels for the Fe-TCPP@Cu-BTC under various discharge stages.\u003c/p\u003e","description":"","filename":"image5.png","url":"https://assets-eu.researchsquare.com/files/rs-4727879/v1/7073cd437a6dfdbe1c01a2e3.png"},{"id":60668540,"identity":"24c3767a-ff88-4b91-9495-c00cb80a7329","added_by":"auto","created_at":"2024-07-19 09:47:36","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":173498,"visible":true,"origin":"","legend":"\u003cp\u003eCatalytic characteristics of enzyme-like Fe-TCPP@Cu-BTC. a) Schematic diagram of \u003cem\u003ein-situ\u003c/em\u003e UV-vis spectroscopy for identifying characteristic signals of different LiPSs during the catalytic process of Fe-TCPP@Cu-BTC. b) \u003cem\u003eIn-situ\u003c/em\u003e UV-vis spectra data recorded at different discharge depth for Fe-TCPP@Cu-BTC. Refinement of the fitting of S\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e*‒\u003c/sup\u003e concentration within a cell containing Fe-TCPP@Cu-BTC by applying Michaelis-Menten kinetics during the discharge at c) 2.8‒2.2 V and d) 2.1‒1.6 V. e) Voltage-dependent activation energy plots collected from EIS spectra at various discharge voltages and temperatures for Fe-TCPP@Cu-BTC and CNTs cells.\u003c/p\u003e","description":"","filename":"image6.png","url":"https://assets-eu.researchsquare.com/files/rs-4727879/v1/088bcdce362d6a79aed8c1ca.png"},{"id":60668575,"identity":"2a6f02a6-96ca-420d-af2a-de5eca623ec8","added_by":"auto","created_at":"2024-07-19 09:47:36","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":321155,"visible":true,"origin":"","legend":"\u003cp\u003eElectrochemical performance of LSBs with Fe-TCPP@Cu-BTC. a) Rate performance of Fe-TCPP@Cu-BTC, Cu-BTC, Fe-TCPP, and CNTs cells. b) Charge-discharge curves of the Fe-TCPP@Cu-BTC cell. Long-term cycling performance of Fe-TCPP@Cu-BTC, Cu-BTC, Fe-TCPP, and CNTs cells at c) 0.2 C and d) 1.0 C. e) Cycling performance of the Fe-TCPP@Cu-BTC cell with a high sulfur loading of 4.5, 5.6, 6.2 mg cm\u003csup\u003e−2\u003c/sup\u003e and an E/S ratio of 6.5 μL m g\u003csup\u003e−1\u003c/sup\u003e. f) Cycling performance of the Fe-TCPP@Cu-BTC pouch cell. e) Part parameters of the Fe-TCPP@Cu-BTC pouch cell.\u003c/p\u003e","description":"","filename":"image7.png","url":"https://assets-eu.researchsquare.com/files/rs-4727879/v1/5d3c55492503e82adbde4351.png"},{"id":63143110,"identity":"14bb9219-ea31-4ba5-918a-e079500211f6","added_by":"auto","created_at":"2024-08-23 15:58:41","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2156920,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4727879/v1/49f2b851-3fcc-46da-8cdf-61fad98fd33b.pdf"},{"id":60669430,"identity":"ee77c0c3-157b-4b8f-8fe5-02307cd8f246","added_by":"auto","created_at":"2024-07-19 09:55:37","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":2883779,"visible":true,"origin":"","legend":"","description":"","filename":"Scheme1.docx","url":"https://assets-eu.researchsquare.com/files/rs-4727879/v1/6f6e97e0ed1487150a1cfb62.docx"},{"id":60668578,"identity":"12cf5e83-98b6-45b9-880e-97aec7485827","added_by":"auto","created_at":"2024-07-19 09:47:36","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":8984029,"visible":true,"origin":"","legend":"","description":"","filename":"SupportingInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-4727879/v1/1c13e04267b97123aa5ebee2.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Spatial-Confinement in Biomimetic Catalysts: Enhancing Homolytic Sulfur-Chain Reactions and Enzyme-like Activity for High-Performance Lithium-Sulfur Batteries","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eLithium-sulfur batteries (LSBs), positioned as the next frontier in energy storage technology, offer several distinct advantages over traditional lithium-ion batteries: superior energy density (2600 Wh kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), cost-effective, and reduced environmental impact, all of which suggest potential for scalable and significantly longer-lasting power sources\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. The functioning of LSBs entails the gradual decomposition of S\u003csub\u003e8\u003c/sub\u003e rings, resulting in the formation of both long-chain and short-chain lithium polysulfides (LiPSs) upon interaction with Li\u003csup\u003e+\u003c/sup\u003e, and ultimately culminates in the production of lithium sulfide (Li\u003csub\u003e2\u003c/sub\u003eS) end products\u003csup\u003e\u003cspan additionalcitationids=\"CR5\" citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u003c/sup\u003e. Nevertheless, LSBs still face several challenges including slow sulfur redox reactions and severe LiPS shuttle effects between the S cathode and the Li anode\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. These issues become particularly critical in practical applications, primarily due to LiPS accumulation under conditions of high sulfur loading and limited electrolyte addition. This accumulation results in severe parasitic reactions at the Li anode, over-saturation precipitation of Li\u003csub\u003e2\u003c/sub\u003eS, and low sulfur utilization efficiency, ultimately impacting the energy density and lifespan of LSBs\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan additionalcitationids=\"CR11\" citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eDeveloping efficient electrocatalytic materials to expedite the conversion of LiPSs represents a promising approach for tackling the aforementioned challenges\u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003e. A prevalent method in this pursuit involves integrating highly conductive carbon materials with metal oxides\u003csup\u003e\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e, \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e, phosphides\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e, sulfides\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e, or nitrides\u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e to establish catalytic centers. These centers facilitate the rapid conversion of LiPSs into insoluble Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003e/Li\u003csub\u003e2\u003c/sub\u003eS at the conductive solid-liquid interface, thereby achieving high sulfur conversion rate\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e. However, the efficacy of this strategy is limited to mitigating shuttle effects within an excessive electrolyte environment. This limitation arises because reduced electrolyte levels substantially elevate the concentrations of long-chain and short-chain LiPSs, which can chemically or electrochemically react with the Li\u003csub\u003e2\u003c/sub\u003eS end product, thereby exacerbating parasitic reactions at the Li anode. Furthermore, the conventional catalysts loaded onto carbon surfaces predominantly exist in nano-/submicron-scale sizes, rendering them susceptible to dissolution or aggregation and leading to a diminished utilization of catalytic sites. Hence, there is an urgent need to identify an efficient catalyst suitable for electrolyte-deficient LSBs.\u003c/p\u003e \u003cp\u003eAfter millions of years of evolution, nature have evolved a series of exquisite and efficient catalytic systems, which provides a good reference for the design of catalytic materials. Cytochrome c oxidase (CcO), consisting of stereo-conformation structure with an inner iron-based heme active center and outer organic ligand layer, is a key component on the inner mitochondrial membrane respiratory chain due to its high oxygen reduction activity\u003csup\u003e\u003cspan additionalcitationids=\"CR21\" citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e. The proton-pumping activity of CcO facilitates the movement of H\u003csup\u003e+\u003c/sup\u003e ions across the mitochondrial membrane, establishing a crucial proton gradient for ATP synthesis\u003csup\u003e\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/sup\u003e. Additionally, the Cu(I) site at the enzyme edge plays a pivotal role in electron transfer to the heme iron atom and the internal Cu(II) site. This results in redox reactions at the Fe/Cu(II) bimetallic center, where coordinated -OH groups are protonated to produce water molecules, creating a cavity between the Fe and Cu(II) sites that enhances the catalysis of subsequent oxidation reactions\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e. In our previous work, we inspired by the high-efficient biological enzyme catalysis system and proposed a periodic expansion catalysis theory which bridge the gap between oxidation catalysis to sulfur catalysis\u003csup\u003e\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/sup\u003e. Based on this guidance, simulating the high-efficient CcO and harnessing the multifunctional Cu active sites and Fe catalytic centers may guide novel biomimetic catalysts design for high-performance LSB systems.\u003c/p\u003e \u003cp\u003eAs for LSBs, the biomimetic catalyst should adjust the structure and composition of natural enzymes to adapt to organic solvent environment and strong electric field environment. Similar to natural enzymes, biomimetic catalysts possess highly dispersed single-atom active sites, stable spatial configurations, and variable local environments, showing a great potential in catalytic conversion of LiPSs. However, in fact, we found that most of these biomimetic enzymes would be dissolved in organic solvents and thus caused active center lost\u003csup\u003e\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u003c/sup\u003e. A good solution is to immobilize them on conductive substrates, such as functionalized carbon nanotubes, graphene, or metal nanowires, which can achieve rapid electron transfer capability. Another important challenge is that the catalytic centers of biomimetic enzymes are easily inactivated by the influence of electrolyte and electric field. Building shells on the biomimetic enzymes may be a good choice to ensure long-term stability and activity, as demonstrated by the encapsulation of metal-organic-frameworks (MOF)\u003csup\u003e\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u003c/sup\u003e, covalent-organic-frameworks (COF)\u003csup\u003e\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e, \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u003c/sup\u003e, and molecular sieves in recent reports\u003csup\u003e\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eIn this study, we developed a biomimetic catalyst of Fe-TCPP@Cu-BTC to mimic the multifunctional Cu active site and iron-based heme catalytic center of CcO (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The catalyst was constructed by encapsulating iron tetrakis(carboxyphenyl)-porphyrin (Fe-TCPP) in copper benzene-1, 3, 5-tricarboxylate (Cu-BTC) MOF, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea, to improve its adaptability and stability in lithium-sulfur chemistry. Through a series of theoretical simulations and experimental tests, we found that Cu-BTC can aggregate a large amount of LiPSs by leveraging its high surface area and strong adsorption capabilities. The Cu atoms within Cu-BTC form bimetallic centers with Fe atoms in Fe-TCPP, promoting the homolytic cleavage of Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003en\u003c/sub\u003e species to into LiS\u003csub\u003en/2\u003c/sub\u003e and accelerating their conversion to Li\u003csub\u003e2\u003c/sub\u003eS. Furthermore, enzyme-like properties were observed in Fe-TCPP@Cu-BTC, which could significantly reduce the activation energy of sulfur conversion rate. The assembled coin LSB exhibited an initial capacity of 1296 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and maintained 885 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e after 100 cycles at a sulfur loading of 5.6 mg cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e and an E/S ratio of 6.5 \u0026micro;L mg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. To further verify its practicality, the pouch cell was assembled with a sulfur loading of 4.0 mg cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e and an E/S ratio of 4 \u0026micro;L mg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. It retained a capacity of 986 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e after 50 cycles, corresponding to an energy density exceeding 300 Wh kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e"},{"header":"2. Results and Discussions","content":"\u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea illustrates the schematic synthesis procedure of Fe-TCPP@Cu-BTC and Cu-BTC by a conventional hydrothermal method\u003csup\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u003c/sup\u003e. The Fe-TCPP@Cu-BTC exhibits regular octahedral crystals, whose morphology is similar to Cu-BTC (Supplementary Fig.\u0026nbsp;1). Element mappings reveals uniform distribution of Cu and Fe atoms in Fe-TCPP@Cu-BTC, suggesting even dispersion of Fe-TCPP molecules within Cu-BTC channels (Supplementary Fig.\u0026nbsp;2). The powder X-ray diffraction (PXRD) reveals no obvious peak shifts from Cu-BTC to Fe-TCPP@Cu-BTC (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb), reconfirming the encapsulation of Fe-TCPP in Cu-BTC frameworks. Based on these findings, Supplementary Fig.\u0026nbsp;3 provided the optimized Fe-TCPP@Cu-BTC molecular model according to the first principle simulations.\u003c/p\u003e \u003cp\u003eFurthermore, Fourier-transform infrared (FT-IR) and UV-vis absorption spectroscopy were used to investigate the chemical interactions between Fe-TCPP and Cu-BTC. As depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec, the featured C-H bonding vibration peak of pyrrole (~\u0026thinsp;1001 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) in Fe-TCPP experienced a higher wavenumber (1003 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) shift upon combination Cu-BTC (Fe-TCPP@Cu-BTC)\u003csup\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e, \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e. This FT-IR finding implies the occurrence of chemical bonding between Fe-TCPP and Cu-BTC. UV-vis absorption spectra in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ed revealed a noticeable shift in the intense Soret band (~\u0026thinsp;420 nm) compared to Fe-TCPP (~\u0026thinsp;416 nm), likely due to depolymerization induced by Cu-BTC and subsequently self-assembly between Fe-TCPP and Cu-BTC\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e. Consequently, nitrogen adsorption-desorption tests yielded a specific surface area of 695.0 m\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for Fe-TCPP@Cu-BTC, slightly lower than the 907.4 m\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e of Cu-BTC (Supplementary Fig.\u0026nbsp;4). In addition, X-ray photoelectron spectroscopy (XPS) was employed to evaluate the impact of Fe-TCPP on the electronic structure of Cu-BTC. Compared to Cu-BTC, the binding energies of Fe-TCPP@Cu-BTC for Cu 2p core levels were up-shifted from 952.2/932.5 to 954.1/934.4 eV and the O 1s core level shifted from 531.5 to 532.3 eV (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ef and Supplementary Fig.\u0026nbsp;5b)\u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e, \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/sup\u003e. On the contrary, the binding energies of Fe 2p core level were down-shifted from 724.8/711.5 to 722.4/710.1 eV, and the N 1s core level shifted from 399.9/397.7 to 400.6/398.8 eV (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eg and Supplementary Fig.\u0026nbsp;5a)\u003csup\u003e\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e, \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e\u003c/sup\u003e. This means the existence of electron transfer from outer Cu-BTC to inner Fe-TCPP in Fe-TCPP@Cu-BTC, which can chemically anchor Fe-TCPP and thereby inhibit its dissolution. Supplementary Fig.\u0026nbsp;6 illustrates the stability of Fe-TCPP@Cu-BTC and Fe-TCPP in a standard LSB electrolyte. It demonstrates that the encapsulation of Fe-TCPP with Cu-BTC effectively prevents Fe-TCPP dissolution. The local solvent environment on the catalyst surface was probed using FT-IR spectroscopy (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ee), where Fe-TCPP@Cu-BTC was immersed in DME for 2 h followed by drying. In this scenario, the peaks at 1110 and 940 cm\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e correspond to the C‒O and O‒Cu bonds of Cu-BTC\u003csup\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u003c/sup\u003e; while the peak at 2878 cm\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e corresponds to the ‒CH\u003csub\u003e3\u003c/sub\u003e group of DME\u003csup\u003e\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e. Upon treatment with DME, the characteristic C‒O and O‒Cu signals of Fe-TCPP@Cu-BTC shifted to 1090 and 917 cm\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, respectively; while the ‒CH\u003csub\u003e3\u003c/sub\u003e signal of DME shifted to 2931 cm\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e. This observation likely originates from dipole-dipole interactions between the solvent and Cu-BTC. As previously reports, these interactions between the catalyst and solvent may facilitate the desolvation of LiPSs, thereby promoting their smooth conversion\u003csup\u003e\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eTo elucidate the behavior of LiPSs within Fe-TCPP@Cu-BTC and to further substantiate our hypothesis, density functional theory (DFT) simulations were conducted to mimic the sequential sulfur transformations throughout the adsorption-catalysis-desorption processes, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. The existence of abundant oxygen-containing functional groups within the Cu-BTC component of the Fe-TCPP@Cu-BTC catalyst facilitates the formation of Li‒O bonds with Li in LiPSs during the reduction process, which in turn attract LiPSs to congregate around the Fe-TCPP@Cu-BTC. Under the influence of an electric field, the Cu-BTC component catalyzes the transformation of Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e8\u003c/sub\u003e into shorter-chain Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e, and their shrunk lengths and reduced volumes enable them to penetrate more readily the cavities of the Fe-TCPP@Cu-BTC\u003csup\u003e\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eUpon entering the cave formed by Fe-TCPP@Cu-BTC, the terminal S (S\u003csub\u003eT\u003c/sub\u003e) atoms of Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e interact with the Cu and Fe components of the Fe-TCPP@Cu-BTC, leading to the formation of Cu-S and Fe-S bonds. Note that this interaction is significantly exothermic by 27.0 kcal/mol, indicating that the encapsulation of Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e in this cavity is thermodynamically favorable and likely to occur spontaneously. The subsequent cleavage of Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e, facilitated by the strain exerted on the sulfur skeleton by the Cu-S and Fe-S bonds (as evidenced by the difference in S-S bond lengths in state I and pristine Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e), may occur through three distinct pathways, denoted as II\u003csub\u003ea\u003c/sub\u003e, II\u003csub\u003eb\u003c/sub\u003e, and II\u003csub\u003ec\u003c/sub\u003e, culminating in the formation of Li-S\u003csub\u003ex\u003c/sub\u003e-M (where x\u0026thinsp;=\u0026thinsp;2, 3, or 4) moieties, respectively. Obviously, the homolytic cleavage leading to the formation of Li-S\u003csub\u003e3\u003c/sub\u003e-M in II\u003csub\u003eb\u003c/sub\u003e is thermodynamically favored over the heterolytic cleavage into Li-S\u003csub\u003ex\u003c/sub\u003e-M (x\u0026thinsp;=\u0026thinsp;2 or 4) (-9.1 kcal/mol vs. -1.2 and 11.0 kcal/mol, respectively, relative to state I), which aligns well with experimental observations and previous reports.\u003c/p\u003e \u003cp\u003eContinuing with a constant supply of Li\u003csup\u003e+\u003c/sup\u003e in the environment, the S\u003csub\u003e3\u003c/sub\u003e moiety within Li-S\u003csub\u003e3\u003c/sub\u003e-M tends to further divide into S\u003csub\u003ey\u003c/sub\u003e and S\u003csub\u003e3\u0026thinsp;\u0026minus;\u0026thinsp;y\u003c/sub\u003e-M (where y\u0026thinsp;=\u0026thinsp;1 or 2), generating dissociative Li\u003csub\u003e2\u003c/sub\u003eS or Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003e species. The production of Li\u003csub\u003e2\u003c/sub\u003eS/LiS\u003csub\u003e2\u003c/sub\u003e-M in IV\u003csub\u003ea\u003c/sub\u003e and Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003ez\u003c/sub\u003e/LiS\u003csub\u003e3\u0026thinsp;\u0026minus;\u0026thinsp;z\u003c/sub\u003e-M (where z\u0026thinsp;=\u0026thinsp;1 or 2) in IV\u003csub\u003eb\u003c/sub\u003e involves energetically more demanding steps by 61.0 and 27.2 kcal/mol, as compared to the less energy-intensive formation of Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003e/LiS-M in IV\u003csub\u003ec\u003c/sub\u003e and Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003ez\u003c/sub\u003e/LiS\u003csub\u003e3\u0026thinsp;\u0026minus;\u0026thinsp;z\u003c/sub\u003e-M (where z\u0026thinsp;=\u0026thinsp;1 or 2) in IV\u003csub\u003ed\u003c/sub\u003e by 16.7 and 17.2 kcal/mol, respectively, with reference to the Li-S\u003csub\u003e3\u003c/sub\u003e-M state denoted as III in this progression. The final cleavage of the remaining S-M bonds in V\u003csub\u003ec\u003c/sub\u003e, facilitated by additional Li\u003csup\u003e+\u003c/sup\u003e, can proceed smoothly through a slightly endothermic step of 7.2 kcal/mol, completing the sulfur reduction process. Conversely, the transformation from IV\u003csub\u003ed\u003c/sub\u003e is thermodynamically quite disfavored. Therefore, the sulfur transformation process is envisioned to proceed in a stepwise manner through stages I \u0026ndash; II\u003csub\u003eb\u003c/sub\u003e \u0026ndash; III \u0026ndash; IV\u003csub\u003ec\u003c/sub\u003e \u0026ndash; V\u003csub\u003ec\u003c/sub\u003e \u0026ndash; VI\u003csub\u003ec\u003c/sub\u003e, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e.\u003c/p\u003e \u003cp\u003eThe interactions between Fe-TCPP@Cu-BTC and LiPSs were further investigated through static adsorption tests. As depicted in \u003cb\u003eSupplementary Fig.\u0026nbsp;7\u003c/b\u003e, the fading of the yellow Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e solution after 12 h of treatment with Fe-TCPP@Cu-BTC, Cu-BTC, Fe-TCPP, and CNTs followed a color depth order of Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e\u0026thinsp;\u0026gt;\u0026thinsp;CNTs\u0026thinsp;\u0026gt;\u0026thinsp;Fe-TCPP\u0026thinsp;\u0026gt;\u0026thinsp;Cu-BTC\u0026thinsp;\u0026gt;\u0026thinsp;Fe-TCPP@Cu-BTC, indicating the highest LiPS absorptivity of Fe-TCPP@Cu-BTC\u003csup\u003e\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u003c/sup\u003e. Subsequently, XPS measurements were conducted to analyze the compositions of the soaked Fe-TCPP@Cu-BTC, Cu-BTC, Fe-TCPP, or CNTs surfaces. As shown in Figs.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea\u003cb\u003e‒c\u003c/b\u003e, distinct Cu 2p and Fe 2p XPS peaks were observed in Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e-treated Fe-TCPP@Cu-BTC (Cu 2p: ~950.8/930.8 eV; Fe 2p: 723.9/710.0 eV), Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e-treated Cu-BTC (Cu 2p: ~953.0/933.1 eV), and Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e-treated Fe-TCPP (Fe 2p: ~724.5/710.9 eV), corresponding to Cu‒S and Fe‒S bond formations resulting from Cu atoms of Cu-BTC, Fe atoms of Fe-TCPP, and S atoms of LiPSs\u003csup\u003e\u003cspan additionalcitationids=\"CR42\" citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/sup\u003e. This observation was corroborated by the S 2p XPS spectra and corresponding deconvolution analysis (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec). The presence of Fe and Cu atoms led to shifts in the binding energies of bridge S (S\u003csub\u003eB\u003c/sub\u003e) and S\u003csub\u003eT\u003c/sub\u003e in Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e-treated Fe-TCPP@Cu-BTC towards higher fields, confirming the formation of Fe‒S and Cu‒S bonds. Moreover, compared to Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e-treated CNTs, the higher binding energy shifts of S\u003csub\u003eB\u003c/sub\u003e and S\u003csub\u003eT\u003c/sub\u003e in Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e-treated Fe-TCPP@Cu-BTC, Cu-BTC, and Fe-TCPP indicated decreased electron density, suggesting the catalyst's mediation of sulfur conversions. Additionally, a lower binding energy shift of Li 1s XPS peaks was observed in Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e-treated Fe-TCPP@Cu-BTC compared to Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e-treated Cu-BTC, Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e-treated Fe-TCPP, and Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e-treated CNTs (Supplementary Fig.\u0026nbsp;8). Consequently, the O 1s and N 1s peaks shifted towards higher binding energy after Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e treatment, indicating strong electron transfer from O and N atoms of Fe-TCPP@Cu-BTC to Li atoms of Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e, leading to Li\u0026middot;\u0026middot;\u0026middot;O and Li\u0026middot;\u0026middot;\u0026middot;N bond formation, known as Li-bonds, according to previous reports (Supplementary Fig.\u0026nbsp;9)\u003csup\u003e\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u003c/sup\u003e. These interactions, mainly through Li-bonds and Fe‒S/Cu‒S bonds, resulted in LiPS enrichment in Fe-TCPP@Cu-BTC and inhibited the shuttle effect of LiPSs.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe catalytic effect of Fe-TCPP@Cu-BTC on LiPSs was extensively investigated through cyclic voltammetry (CV) tests in a symmetrical battery employing Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e electrolyte (Supplementary Fig.\u0026nbsp;10). Fe-TCPP@Cu-BTC cells exhibited a significantly higher current density compared to Cu-BTC, Fe-TCPP, and CNTs, indicative of substantially improved redox kinetics of LiPSs by Fe-TCPP@Cu-BTC. Electrochemical reactivity was further assessed via CV analysis. Supplementary Fig.\u0026nbsp;11a‒d illustrates the initial CV profiles of cells with Fe-TCPP@Cu-BTC, Cu-BTC, Fe-TCPP, and CNTs at a rate of 0.1 mV s\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, revealing two major peaks at ~\u0026thinsp;2.31 and 2.05 V, corresponding to the reduction of S\u003csub\u003e8\u003c/sub\u003e to soluble long-chain LiPS (Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003en\u003c/sub\u003e, 4\u0026thinsp;\u0026le;\u0026thinsp;n\u0026thinsp;\u0026le;\u0026thinsp;8), and further to solid Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003e/Li\u003csub\u003e2\u003c/sub\u003eS, respectively. The oxidation peaks at ~\u0026thinsp;2.42 V are attributed to the conversion from Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003e/Li\u003csub\u003e2\u003c/sub\u003eS to Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003en\u003c/sub\u003e and S\u003csub\u003e8\u003c/sub\u003e. Comparing with other control cells, the CV curve of the Fe-TCPP@Cu-BTC cell displays a distinct positive shift of the cathodic peak and negative shift of the anodic peak (Supplementary Fig.\u0026nbsp;12a‒b), indicating reduced voltage polarization and enhanced reaction kinetics influenced by Fe-TCPP@Cu-BTC.\u003c/p\u003e \u003cp\u003eFurthermore, sulfur redox kinetics were quantitatively evaluated using Tafel slopes based on each individual process (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea‒b and Supplementary Fig.\u0026nbsp;13). The Fe-TCPP@Cu-BTC cell also demonstrated the smallest value of 28.3, 33.4, and 43.7 mV dec\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e at S\u003csub\u003e8\u003c/sub\u003e\u0026rarr;Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003en\u003c/sub\u003e, Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003en\u003c/sub\u003e\u0026rarr;Li\u003csub\u003e2\u003c/sub\u003eS, and Li\u003csub\u003e2\u003c/sub\u003eS\u0026rarr;Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003en\u003c/sub\u003e conversions, respectively, compared to Cu-BTC (32.3, 52.6, and 85.1 mV dec\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e), Fe-TCPP (38.4, 62.3, and 111.7 mV dec\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e), and CNTs (41.9, 70.9, and 132.7 mV dec\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e). These results highlight the excellent redox reaction kinetics behaviors and electrochemical reversibility of Fe-TCPP@Cu-BTC. Additionally, the Li\u003csup\u003e+\u003c/sup\u003e diffusion coefficient in each cathode was quantified using CV tests under various scan rates ranging from 0.10 to 0.30 mV s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Plots in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed, Supplementary Fig.\u0026nbsp;14, and Supplementary Fig.\u0026nbsp;15a‒c indicate that the peaks for cells with Fe-TCPP@Cu-BTC are much more intense than those for the other three cells, suggesting promoted LiPS conversions by Fe-TCPP@Cu-BTC. The Li ion diffusion properties were estimated using the classical Randles-Sevcik equation. The cells with Fe-TCPP@Cu-BTC exhibited larger slopes of lithium-ion diffusion coefficient (P\u003csub\u003eA\u003c/sub\u003e = 3.24 \u0026times; 10\u003csup\u003e‒9\u003c/sup\u003e; P\u003csub\u003eB\u003c/sub\u003e = 1.30 \u0026times; 10\u003csup\u003e‒8\u003c/sup\u003e; P\u003csub\u003eC\u003c/sub\u003e = 2.65 \u0026times; 10\u003csup\u003e‒8\u003c/sup\u003e cm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e s\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e) compared to Cu-BTC (2.95 \u0026times; 10\u003csup\u003e‒9\u003c/sup\u003e; 6.39 \u0026times; 10\u003csup\u003e‒9\u003c/sup\u003e; 1.83 \u0026times; 10\u003csup\u003e‒8\u003c/sup\u003e cm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e s\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e), Fe-TCPP (2.06 \u0026times; 10\u003csup\u003e‒9\u003c/sup\u003e; 5.97 \u0026times; 10\u003csup\u003e‒9\u003c/sup\u003e; 1.51 \u0026times; 10\u003csup\u003e‒8\u003c/sup\u003e cm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e s\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e), and CNTs (1.40 \u0026times; 10\u003csup\u003e‒9\u003c/sup\u003e; 5.52 \u0026times; 10\u003csup\u003e‒9\u003c/sup\u003e; 7.94 \u0026times; 10\u003csup\u003e‒9\u003c/sup\u003e cm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e s\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e), demonstrating enhanced LiPS conversion kinetics of Fe-TCPP@Cu-BTC throughout the charge/discharge processes. Nucleation Transformation Ratio (NTR) was used to assess the kinetics behaviors of the cathode reactions\u003csup\u003e\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u003c/sup\u003e. All NTR values for Fe-TCPP@Cu-BTC cells at different scan rates were close to 3, indicating rapid transformation of LiPSs to Li\u003csub\u003e2\u003c/sub\u003eS facilitated by Fe-TCPP@Cu-BTC (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eg).\u003c/p\u003e \u003cp\u003eThe process of converting LiPSs to Li\u003csub\u003e2\u003c/sub\u003eS during discharge accounts for three-quarters of the theoretical capacity, underscoring the importance of enhancing kinetics in this phase. To investigate the impact of Fe-TCPP@Cu-BTC on this conversion, we conducted potentiostatic intermittent titration technique (PITT) tests on cells, focusing on liquid\u0026ndash;solid conversion kinetics (see Supplementary Fig.\u0026nbsp;16). Generally, PITT discharge curves exhibit two distinct regions: the first involves liquid-liquid conversion from long-chain to short-chain LiPS, while the second region entails liquid-solid conversion, corresponding to Li\u003csub\u003e2\u003c/sub\u003eS deposition. In the initial process, the addition of Fe-TCPP@Cu-BTC led to notable enhancements in initial current responses, with increases of 55% (Cu-BTC), 134% (Fe-TCPP), and 228% (CNTs) at each potentiostatic step, indicating improved liquid-liquid conversion kinetics. Subsequently, during the second process, the Li\u003csub\u003e2\u003c/sub\u003eS deposition peak time was earliest for the Fe-TCPP@Cu-BTC cell (1970 s), indicative of a faster deposition rate\u003csup\u003e\u003cspan additionalcitationids=\"CR46\" citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/sup\u003e. Further Li\u003csub\u003e2\u003c/sub\u003eS nucleation tests were conducted, with results detailed in Supplementary Fig.\u0026nbsp;16. According to Faraday\u0026rsquo;s law, deposition capacities on Fe-TCPP@Cu-BTC, Cu-BTC, Fe-TCPP, and CNTs electrodes were measured at 236.9, 182.9, 175.7, and 142.6 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively\u003csup\u003e\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e\u003c/sup\u003e. These findings highlight the ability of Fe-TCPP@Cu-BTC to inhibit shuttle effects and enhance sulfur utilization, thereby enabling high-capacity Li\u003csub\u003e2\u003c/sub\u003eS precipitations.\u003c/p\u003e \u003cp\u003eDynamic monitoring techniques were employed to trace the sulfur evolution features. In-situ ultraviolet‒visible (UV‒Vis) absorption spectra of four cells: Fe-TCPP@Cu-BTC, Cu-BTC, Fe-TCPP, and CNTs are depicted in Supplementary Fig.\u0026nbsp;18‒19. Each cell exhibits characteristic absorption peaks at approximately 492, 475, 420, and 617 nm, corresponding to S\u003csub\u003e8\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e, S\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e, S\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e, and S\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e/S\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e*\u0026minus;\u003c/sup\u003e anions, respectively. During discharge, the Fe-TCPP@Cu-BTC cell demonstrated the most rapid decrease in S\u003csub\u003e8\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e intensity compared to other cells in the Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e8\u003c/sub\u003e electrolyte (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea)\u003csup\u003e\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u003c/sup\u003e. Moreover, the intensity of S\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e2‒\u003c/sup\u003e/S\u003csub\u003e3\u003c/sub\u003e*\u003csup\u003e‒\u003c/sup\u003e initially increased followed by a decrease, indicating its role as an intermediate bridge for Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003e/Li\u003csub\u003e2\u003c/sub\u003eS formation. A similar trend was observed in the Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e4\u003c/sub\u003e electrolyte (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb), suggesting the capability of Fe-TCPP@Cu-BTC catalyst to promote both long-chain and short-chain LiPS conversion, along with Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003e/Li\u003csub\u003e2\u003c/sub\u003eS generation. Notably, unlike other samples, the Fe-TCPP sample exhibited an additional absorption peak at 430 nm, which is the characteristic of porphyrin iron, further confirming Fe-TCPP's tendency to dissolve in the electrolyte.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo gain a deeper insight into the catalytic effect of Fe-TCPP@Cu-BTC on sulfur species transformation, \u003cem\u003ein-situ\u003c/em\u003e Raman spectra were measured (Figs.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec‒f, Supplementary Fig.\u0026nbsp;20). Without a catalyst (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ef, Supplementary Fig.\u0026nbsp;20d), only the S\u003csub\u003e8\u003c/sub\u003e/Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e8\u003c/sub\u003e peak (152, 246, 437, 472 cm\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e) was observed, persisting even after discharge to 1.6 V, indicating incomplete sulfur reduction, which leads to the poor CNT cell performance. However, with Fe-TCPP@Cu-BTC, the intensity of the S\u003csub\u003e8\u003c/sub\u003e/Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e8\u003c/sub\u003e peak gradually decreased during discharge. By 2.5 V discharge, peaks of S\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e2‒\u003c/sup\u003e (325 cm\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e) and S\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2‒\u003c/sup\u003e (496 cm\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e) emerged, while the S\u003csub\u003e8\u003c/sub\u003e/Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e8\u003c/sub\u003e peak vanished, indicating decomposition into Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e and Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e4\u003c/sub\u003e. When discharging to 2.0 V, Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e vanished, replaced by a Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e4\u003c/sub\u003e peak (496 cm\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e), along with a small amount of S\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e2‒\u003c/sup\u003e/S\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e*‒\u003c/sup\u003e (534 cm\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e) and Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003e (510 cm\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e). Upon discharge to 1.6 V, Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e4\u003c/sub\u003e and S\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e2‒\u003c/sup\u003e/S\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e*‒\u003c/sup\u003e were consumed, yielding Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003e and Li\u003csub\u003e2\u003c/sub\u003eS (375 cm\u003csup\u003e‒\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e), indicating complete conversion of S\u003csub\u003e8\u003c/sub\u003e/Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e8\u003c/sub\u003e to Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003e/Li\u003csub\u003e2\u003c/sub\u003eS\u003csup\u003e49\u0026ndash;51\u003c/sup\u003e. The Cu-BTC cell (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed, Supplementary Fig.\u0026nbsp;20b) exhibited slower disappearance or generation of sulfur species compared to the Fe-TCPP@Cu-BTC cell. Notably, the S\u003csub\u003e8\u003c/sub\u003e/Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e8\u003c/sub\u003e peak vanished at 2.3 V, while complete consumption and generation of S\u003csub\u003e8\u003c/sub\u003e/Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e, Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e3\u003c/sub\u003e/Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e4\u003c/sub\u003e occurred at 2.4 V, 2.1 V, 1.8 V, and 1.9 V, respectively, along with a small production of Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003e. Moreover, the solubility of Fe-TCPP in the electrolyte could cause catalyst loss, reducing sulfur reaction kinetics. In the Fe-TCPP cell (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ee, Supplementary Fig.\u0026nbsp;20c), only the disappearance of S\u003csub\u003e8\u003c/sub\u003e/Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e8\u003c/sub\u003e (2.1 V) and generation of Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e were detected. Thus, the addition of Fe-TCPP@Cu-BTC catalyst facilitated sulfur species reduction via homolysis, increasing the sulfur reduction pathways and ensuring rapid and complete sulfur conversion.\u003c/p\u003e \u003cp\u003eThe \u003cem\u003esemi-in-situ\u003c/em\u003e analysis of Cu 2p and Fe 2p XPS spectra further elucidated the catalytic mechanisms, as depicted in Figs.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eg‒h. Evidently, the Cu 2p\u003csub\u003e1/2\u003c/sub\u003e, Cu 2p\u003csub\u003e3/2\u003c/sub\u003e, and Cu‒S peaks associated with Cu-BTC for the Fe-TCPP@Cu-BTC cell gradually shifted to lower binding energies (Cu 2p\u003csub\u003e1/2\u003c/sub\u003e/Cu 2p\u003csub\u003e3/2\u003c/sub\u003e and Cu‒S; 2.8 V: 954.1/933.5 eV and 952.0/932.0 eV; 2.1 V: 953.4/933.1 eV and 951.6/931.8 eV; 1.6 V: 953.7/932.6 eV and 951.3/930.7 eV, respectively) compared to the Cu-BTC cell (Cu 2p\u003csub\u003e1/2\u003c/sub\u003e/Cu 2p\u003csub\u003e3/2\u003c/sub\u003e and Cu‒S; 2.8 V: 954.4/934.4 eV and 952.8/933.7 eV; 2.1 V: 954.3/934.4 eV and 952.8/933.3 eV; 1.6 V: 953.9/933.9 eV and 952.6/933.0 eV, Supplementary Fig.\u0026nbsp;21a). Similar observations were made for the Fe 2p\u003csub\u003e1/2\u003c/sub\u003e, Fe 2p\u003csub\u003e3/2\u003c/sub\u003e, and Fe‒S peaks in Fe-TCPP@Cu-BTC (Fe 2p\u003csub\u003e1/2\u003c/sub\u003e/ Fe 2p\u003csub\u003e3/2\u003c/sub\u003e and Fe‒S; 2.8 V: 727.7/714.0 eV and 725.7/712.1 eV; 2.1 V: 727.4/713.9 eV and 724.3/711.4 eV; 1.6 V: 727.0/712.9 eV and 724.0/710.8 eV, respectively) and Fe-TCPP cell (Fe 2p\u003csub\u003e1/2\u003c/sub\u003e/ Fe 2p\u003csub\u003e3/2\u003c/sub\u003e and Fe‒S; 2.8 V: 728.3/714.3 eV and 726.7/712.3 eV; 2.1 V: 728.1/714.3 eV and 725.9/712.0 eV; 1.6 V: 727.9/714.3 eV and 725.8/711.9 eV, Supplementary Fig.\u0026nbsp;21b)\u003csup\u003e\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e, \u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e\u003c/sup\u003e. The lower binding energy shifts of Fe‒S and Cu‒S bonds during the discharge process suggest enhanced interactions between Cu and S, and Fe and S atoms, facilitating the breakage of S‒S bonds from long-chain to short-chain LiPSs. Moreover, the Cu‒S and Fe‒S bonds between LiPSs and Fe-TCPP@Cu-BTC led to a gradual increase in the electron cloud density around Cu and Fe atoms, which contributing to S‒S bond breaking.\u003c/p\u003e \u003cp\u003eTo reveal the enzymatic catalysis mechanism of Fe-TCPP@Cu-BTC, a steady-state kinetic analysis was conducted by varying the concentration of S\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e*‒\u003c/sup\u003e within a fixed concentration of Fe-TCPP@Cu-BTC by \u003cem\u003ein-situ\u003c/em\u003e UV‒Vis spectra, which exhibited conformity with the classic Michaelis‒Menten kinetics throughout all stages of discharge processes (Figs.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec‒d). The Michaelis‒Menten plots provided values for the enzyme kinetic parameters of Michaelis‒Menten constants (\u003cem\u003eK\u003c/em\u003e\u003csub\u003e\u003cem\u003em\u003c/em\u003e\u003c/sub\u003e), where \u003cem\u003eK\u003c/em\u003e\u003csub\u003e\u003cem\u003em\u003c/em\u003e\u003c/sub\u003e reflects the affinity of the biomimetic enzyme towards the substrate (lower \u003cem\u003eK\u003c/em\u003e\u003csub\u003e\u003cem\u003em\u003c/em\u003e\u003c/sub\u003e indicates a higher affinity) and \u003cem\u003eV\u003c/em\u003e\u003csub\u003e\u003cem\u003emax\u003c/em\u003e\u003c/sub\u003e indicates the catalytic activity of the biomimetic enzyme. Compared to Cu-BTC (fitting the equation within 2.5\u0026ndash;2.2 V with \u003cem\u003eK\u003c/em\u003e\u003csub\u003e\u003cem\u003em\u003c/em\u003e\u003c/sub\u003e = 1.02\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e mM) and Fe-TCPP (fitting the equation within 2.1\u0026ndash;1.6 V with \u003cem\u003eK\u003c/em\u003e\u003csub\u003e\u003cem\u003em\u003c/em\u003e\u003c/sub\u003e = 3.89\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e mM), Fe-TCPP@Cu-BTC exhibits consistently smaller \u003cem\u003eK\u003c/em\u003e\u003csub\u003e\u003cem\u003em\u003c/em\u003e\u003c/sub\u003e values throughout the entire sulfur conversion range (2.8\u0026ndash;2.2 V, \u003cem\u003eK\u003c/em\u003e\u003csub\u003e\u003cem\u003em\u003c/em\u003e\u003c/sub\u003e = 5.92\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e mM; 2.1\u0026ndash;1.6 V, \u003cem\u003eK\u003c/em\u003e\u003csub\u003e\u003cem\u003em\u003c/em\u003e\u003c/sub\u003e = 7.79\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;4\u003c/sup\u003e mM) (see Supplementary Table\u0026nbsp;1). In contrast, CNTs did not exhibit conformity with this kinetics (Supplementary Fig.\u0026nbsp;22). These findings indicate that the Fe-TCPP@Cu-BTC biomimetic enzyme exhibits higher affinity, which is consistent with LiPS adsorption findings (see Supplementary Fig.\u0026nbsp;7). Furthermore, \u003cem\u003eV\u003c/em\u003e\u003csub\u003e\u003cem\u003emax\u003c/em\u003e\u003c/sub\u003e was determined at different sulfur conversion segments. The Fe-TCPP@Cu-BTC (2.8\u0026ndash;2.2 V: \u003cem\u003eV\u003c/em\u003e\u003csub\u003e\u003cem\u003emax\u003c/em\u003e\u003c/sub\u003e = 5.87\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;4\u003c/sup\u003e mM min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e; 2.1\u0026ndash;1.6 V: \u003cem\u003eV\u003c/em\u003e\u003csub\u003e\u003cem\u003emax\u003c/em\u003e\u003c/sub\u003e = 1.87\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;4\u003c/sup\u003e mM min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) is about two orders of magnitude higher than that of Fe-TCPP (2.5\u0026ndash;2.2 V: \u003cem\u003eV\u003c/em\u003e\u003csub\u003e\u003cem\u003emax\u003c/em\u003e\u003c/sub\u003e = 8.47\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;6\u003c/sup\u003e mM min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and Cu-BTC (2.1\u0026ndash;1.6 V: \u003cem\u003eV\u003c/em\u003e\u003csub\u003e\u003cem\u003emax\u003c/em\u003e\u003c/sub\u003e = 1.24\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;6\u003c/sup\u003e mM min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) (see Supplementary Table\u0026nbsp;2). This suggests that the homolytic reaction of LiPSs under the influence of this biomimetic enzyme can increase the sulfur conversion rate by nearly 100 times.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo disclose the kinetic improvements in sulfur redox reactions, the activation barrier at specific voltages was experimentally determined. This was achieved by fitting the charge transfer resistance measured at various temperatures using electrochemical impedance spectroscopy (EIS), to the activation energy (\u003cem\u003eE\u003c/em\u003e\u003csub\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sub\u003e) (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ee and Supplementary Fig.\u0026nbsp;23\u0026ndash;28). The Fe-TCPP@Cu-BTC cell exhibited a significantly lower \u003cem\u003eE\u003c/em\u003e\u003csub\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sub\u003e value (0.29\u0026ndash;1.03 eV) compared to Cu-BTC (0.34\u0026ndash;1.20 eV), Fe-TCPP (0.38\u0026ndash;1.25 eV), and CNTs (0.55\u0026ndash;1.42 eV) cells within the voltage range of 2.4\u0026ndash;1.6 V. These results demonstrate that Fe-TCPP@Cu-BTC can catalyze the conversion of both long-chain and short-chain LiPSs more effectively\u003csup\u003e\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eThe rate performance demonstrates that the Fe-TCPP@Cu-BTC cell delivers superior discharge capacities of 1522, 1162, 1079, 1024, and 970 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e at 0.2, 0.5, 1.0, 1.5, and 2.0 C, respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea). When the rate returns to 1.5, 1.0, 0.5, and 0.2 C, the reversible capacities are restored to 1000, 1023, 1054, and 1189 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively. In contrast, the control cells exhibit significant fluctuation and a general attenuation trend with changing rates. The improved performance of the Fe-TCPP@Cu-BTC cell indicates a kinetically efficient reaction process with fast electron transfer. Additionally, the galvanostatic charge-discharge curves of the Fe-TCPP@Cu-BTC electrode at various C-rates (0.2\u0026ndash;2.0 C) are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eb, revealing that the polarization of the charge-discharge curves increases slightly with higher C-rates. The decreased overpotential, superior rate capability, and high reversibility of the Fe-TCPP@Cu-BTC cell result from improved electrochemical kinetics, as further revealed by electrochemical impedance spectroscopy (EIS). Supplementary Fig.\u0026nbsp;29 illustrates the impedance for both control and Fe-TCPP@Cu-BTC cells after 0, 3, and 10 cycles. After 10 cycles, the R\u003csub\u003ee\u003c/sub\u003e (resistance of electrolyte), R\u003csub\u003ect\u003c/sub\u003e (resistance of charge transfer), and R\u003csub\u003emt\u003c/sub\u003e (resistance of mass transfer) of the Fe-TCPP@Cu-BTC cell remain similar to those at 3 cycles, indicating continuous cycling stability of electrons/ions and improved sulfur utilization. It is reasonable to speculate that a solid electrolyte interphase (SEI) film forms after three cycles in the Fe-TCPP@Cu-BTC cell. Detailed impedance data is provided in Supplementary Tables\u0026nbsp;1‒4.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eMoreover, the Fe-TCPP@Cu-BTC catalyst exhibits excellent long-term cycling performance for the Li\u0026ndash;S cell. Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ec and Supplementary Fig.\u0026nbsp;30 shows that the Fe-TCPP@Cu-BTC cell delivers a high initial discharge capacity of 1548 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e at 0.2 C, maintaining 935 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e after 150 cycles. In contrast, the control cells (Cu-BTC, Fe-TCPP, and CNTs) deliver initial capacities of 1406, 1395, and 1298 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, maintaining 733, 574, and 448 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e after 150 cycles, respectively. The cycling stability of these cells was further measured at 1.0 C. Compared with Cu-BTC (0.056%), Fe-TCPP (0.075%), and CNTs (0.111%), the Fe-TCPP@Cu-BTC cell shows the highest capacity retention (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ed, Supplementary Fig.\u0026nbsp;31) and the lowest capacity decay (0.043% per cycle) with an initial discharge capacity of over 1016 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and maintaining 751 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e after 600 cycles. Furthermore, higher sulfur loadings of 4.5, 5.6, and 6.2 mg cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e were tested under an electrolyte/sulfur (E/S) ratio of 6.5 \u0026micro;L mg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, with initial discharge capacities of 1350, 1296, and 1280 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, fading to 976, 885, and 682 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e after 100 cycles (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ee). The superior stabilization effect of Fe-TCPP@Cu-BTC is confirmed by the pouch cell (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ef), which exhibited a high initial discharge capacity of 5.2 mAh cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e (1435 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) with a sulfur loading of 4.0 mg cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e and an E/S ratio controlled at 4 \u0026micro;L mg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. After 50 cycles, the capacity still maintains above 3.7 mAh cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e (986 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e). The pouch cell performance parameters for the first discharge cycle are summarized in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eg, showing a high specific discharge capacity of 1299 mA h g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, providing a total discharge capacity of 0.104 Ah. The average voltage was 2.19 V, and the discharge energy of the pouch cell was 0.228 Wh. Based on the total mass, the actual energy density of the pouch cell was calculated to be 300.4 Wh kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e"},{"header":"3. Conclusion","content":"\u003cp\u003eIn this study, we developed a biomimetic catalyst, Fe-TCPP@Cu-BTC, to emulate the multifunctional Cu active site and the iron-based heme catalytic center of cytochrome c oxidase. Through a series of theoretical simulations and experimental analyses, we found that Cu-BTC can aggregate a large amount of LiPSs due to its high surface area and strong adsorption capabilities. The Cu-Fe bimetallic center within the spatially confined Fe-TCPP@Cu-BTC significantly promotes the homolytic cleavage of Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e to LiS\u003csub\u003e3\u003c/sub\u003e and accelerates their subsequent conversion to Li\u003csub\u003e2\u003c/sub\u003eS. The enzyme-like properties were further evaluated using Michaelis-Menten kinetics, confirming that the homolytic reaction can increase the sulfur conversion rate by nearly 100-fold. As a result, the Fe-TCPP@Cu-BTC-based coin-type LSB with a sulfur loading of 5.6 mg cm⁻\u0026sup2; and an E/S ratio of 6.5 \u0026micro;L mg⁻\u0026sup1; exhibited an initial capacity of 1296 mAh g⁻\u0026sup1; at 0.1 C and maintained 885 mAh g⁻\u0026sup1; after 100 cycles. To further verify its practicality, a pouch cell was assembled with a sulfur loading of 4.0 mg cm⁻\u0026sup2; and an E/S ratio of 4 \u0026micro;L mg⁻\u0026sup1;. It retained a capacity of 986 mAh g⁻\u0026sup1; after 50 cycles, corresponding to an energy density exceeding 300 Wh kg⁻\u0026sup1;. This work opens up new possibilities for catalyst design in energy storage systems, potentially leading to breakthroughs in other areas of electrochemistry and materials science. It underscores the value of drawing inspiration from nature\u0026rsquo;s efficient catalytic systems to solve complex technological challenges.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eSupporting Information\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSupporting Information is available from the Wiley Online Library or from the author.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis research was funded in part by Natural Science Foundation of Zhejiang Province (Grant No. LQ22B030003 and LY22B030002), National Natural Science Foundation of China (Grant Nos. 22309136, 22109119, 51972238), Major Scientific and Technological Innovation Project of Wenzhou City (Grant No. ZG2021013) and Xinmiao Foundation of Zhejiang Province (Grant No. 2024R429B042).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConflicts of Interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThere are no conflicts to declare.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData Availability Statement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eResearch data are not shared.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor Contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eT.L., Y. Dong and Z.G. contributed equally to this work. T. L. performed all the experiments with the assistance of M.S., S.Y., M.Z. and H.N., J.G. and H.T.. D.C.analyzed the data and prepared the results. Z.G., J.G. and H.T. conducted the MD simulations and the theoretical calculations. D.C. and H.T. planned the study and composed the manuscript. Z.Y. conceived and supervised the project.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eLi C et al (2024) Three Birds with One Stone: Multifunctional Separators Based on SnSe Nanosheets Enable High-Performance Li‐, Na‐ and K‐Sulfur Batteries. Adva Energy Mater\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhao C et al (2023) The Origin of Strain Effects on Sulfur Redox Electrocatalyst for Lithium Sulfur Batteries. 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J Am Chem Soc 141:11093\u0026ndash;11102\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWang X et al (2020) Confined Fe-Cu Clusters as Sub-Nanometer Reactors for Efficiently Regulating the Electrochemical Nitrogen Reduction Reaction. Adv Mater 32:e2004382\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eDong Y et al (2024) Dynamic Stereo-Conformation of Catalyst‐In‐Cavity Biomimetic Enzymes Enable High‐Sulfur‐Utilization and Lean‐Electrolyte Lithium‐Sulfur Batteries. Adv Funct Mater 2406455\u003c/span\u003e\u003c/li\u003e\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":"lithium − sulfur battery, iron porphyrin, metal-organic-framework, spatial confinement, enzymatic catalysis, lithium polysulfide homolytic reaction","lastPublishedDoi":"10.21203/rs.3.rs-4727879/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4727879/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe most burning issue for high-energy-density lithium-sulfur batteries is developing high-efficient catalyst to address sulfur reaction kinetics and lithium polysulfide shuttling effects. In this work, we present Fe-TCPP@Cu-BTC, a biomimetic catalyst that mimics cytochrome c oxidase, by encapsulating porphyrin-based small molecules into metal-organic frameworks, for high-performance lithium-sulfur batteries. Through a series of \u003cem\u003ein-situ\u003c/em\u003e spectroscopic analyses and theoretical simulations, it was found that the Cu-Fe bimetallic center within the spatially confined Fe-TCPP@Cu-BTC significantly promotes the homolytic cleavage of Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e to LiS\u003csub\u003e3\u003c/sub\u003e, and accelerates their subsequent conversion to Li\u003csub\u003e2\u003c/sub\u003eS. The enzyme-like properties were further evaluated using Michaelis-Menten kinetics, confirming that the homolytic reaction can increase the sulfur conversion rate by nearly 100-fold. As a result, the pouch lithium-sulfur batteries delivered an energy density exceeding 300 Wh/kg. This work demonstrates the tremendous potential of component and structural regulation of biomimetic enzymes in the conversion reactions of metal-sulfur batteries.\u003c/p\u003e","manuscriptTitle":"Spatial-Confinement in Biomimetic Catalysts: Enhancing Homolytic Sulfur-Chain Reactions and Enzyme-like Activity for High-Performance Lithium-Sulfur Batteries","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-07-19 09:47:31","doi":"10.21203/rs.3.rs-4727879/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":"9ad36758-de65-4fa7-a19b-54008132c86d","owner":[],"postedDate":"July 19th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":34766182,"name":"Physical sciences/Chemistry/Electrochemistry/Batteries"},{"id":34766183,"name":"Physical sciences/Chemistry/Catalysis/Electrocatalysis"}],"tags":[],"updatedAt":"2024-08-23T15:50:34+00:00","versionOfRecord":[],"versionCreatedAt":"2024-07-19 09:47:31","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-4727879","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4727879","identity":"rs-4727879","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}