Reaction Energy Barrier Research Articles

Recent Advances in Transition Metal Chalcogenides Electrocatalysts for Oxygen Evolution Reaction in Water Splitting

Rapid industrial growth has overexploited fossil fuels, making hydrogen energy a crucial research area for its high energy and zero carbon emissions. Water electrolysis is a promising method as it is greenhouse gas-free and energy-efficient. However, OER, a slow multi-electron transfer process, is the limiting step. Thus, developing efficient, low-cost, abundant electrocatalysts is vital for large-scale water electrolysis. In this paper, the application and progress of transition metal chalcogenides (TMCs) as catalysts for the oxygen evolution reaction in recent years are comprehensively reviewed. The key findings highlight the catalytic mechanism and performance of TMCs synthesized using single or multiple transition metals. Notably, modifications through recombination, heterogeneous interface engineering, vacancy, and atom doping are found to effectively regulate the electronic structure of metal chalcogenides, increasing the number of active centers and reducing the adsorption energy of reaction intermediates and energy barriers in OER. The paper further discusses the shortcomings and challenges of TMCs as OER catalysts, including low electrical conductivity, limited active sites, and insufficient stability under harsh conditions. Finally, potential research directions for developing new TMC catalysts with enhanced efficiency and stability are proposed.

Surface-hydrogenated CrMnOx coupled with GaN nanowires for light-driven bioethanol dehydration to ethylene

Light-driven bioethanol dehydration offers attractive outlooks for the sustainable production of ethylene. Herein, a surface-hydrogenated CrMnOx is coupled with GaN nanowires (GaN@CMO-H) for light-driven ethanol dehydration to ethylene. Through combined experimental and computational investigations, a surface hydrogen-replenishment mechanism is proposed to disclose the ethanol dehydration pathway over GaN@CMO-H. Moreover, the surface-hydrogenated GaN@CMO-H can significantly lower the reaction energy barrier of the C2H5OH-to-C2H4 conversion by switching the rate-determining reaction step compared to both GaN and GaN@CMO. Consequently, the surface-hydrogenated GaN@CMO-H illustrates a considerable ethylene production activity of 1.78 mol·gcat−1·h−1 with a high turnover number of 94,769 mole ethylene per mole CrMnOx. This work illustrates a new route for sustainable ethylene production with the only use of bioethanol and sunlight beyond fossil fuels.

Fine-tunable N-doping in carbon-coated CoFe nano-cubes for efficient hydrogen evolution in AEM water electrolysis

To obtain environment-friendly and renewable hydrogen energy, research is being actively conducted towards lowering the hydrogen evolution reaction (HER) energy barrier through various modifications to the surface of a transition metal bimetal electrochemical catalyst. Herein, we report the development of highly N-doped carbon shell-encapsulated cobalt iron nano cube (CoFe@HNCS) through fine-tuning of the nitrogen-doping content in the carbon shell. The pyridinic N-rich N-doped carbon shell, achieved by adding melamine through electrostatic interactions, improves conductivity, increases active sites, and optimizes Gibbs free energy for hydrogen adsorption. In alkaline HER performance, the optimized CoFe@HNC20 exhibits a lower overpotential (98.2 mV) than CoFe@NCS (133.2 mV) at 10 mA cm−2. Furthermore, CoFe@HNCS20 as cathode catalyst in anion exchange membrane (AEM) water electrolyzer also shows low cell voltage of 1.808 V to achieve the current density of 0.5 A cm−2. The expansion of the application to combine solar cells and AEM electrolyzer suggests the possibility of a hydrogen ecosystem.

Nitrogen-Doped Porous Nanofiber Aerogel-Encapsulated Staphylo-Ni3S2 Accelerating Polysulfide Conversion for Efficient Li-S Batteries.

The low conductivity of sulfur substances and the fussy effect of lithium polysulfides (LPS) limit the practical application of lithium-sulfur batteries (LSBs). In this work, Ni3S2 is in situ synthesized on N-doped 3D carbon nanofibers with an optimized pore structure as a cathode material for LSBs. The conductive carbon nanofiber skeleton with a hierarchical (micropore-mesopore-macropore) structure etched by Cd2+ can reduce the interface resistance of the cathode and remiss volume expansion during charge-discharge progress. The Ni was vulcanized and nitrogen-doped successively during the annealing process. In addition, the polar Ni3S2 and N-doped carbon structure can promote the catalytic conversion of LPS and regulate the 3D nucleation of Li2S, which could reduce the reaction energy barrier. Therefore, the NCF-Cd-Ni3S2-NC cathode can maintain a high initial capacity (1080.2 mAh g-1) and excellent stability at 0.1C. This work provides an important basis for the synthesis of high efficiency and inexpensive cathode carrier materials for LSBs.

Interfacial Water Orientation in Neutral Oxygen Catalysis for Reversible Ampere-Scale Zinc-Air Batteries.

The neutral oxygen catalysis is an electrochemical reaction of the utmost importance in energy generation, storage application, and chemical synthesis. However, the restricted availability of protons poses a challenge to achieving kinetically favorable oxygen catalytic reactions. Here, we alter the interfacial water orientation by adjusting the Brønsted acidity at the catalyst surface, to break the proton transfer limitation of neutral oxygen electrocatalysis. An unexpected role of water molecules in improving the activity of neutral oxygen catalysis is revealed, namely, increasing the H-down configuration water in electric double layers rather than merely affecting the energy barriers for reaction limiting steps. The proposed porous nanofibers with atomically dispersed MnN3 exhibit record-breaking activity (EORR@1/2/EOER@10 mA = 0.85/1.65 V vs. RHE) and reversibility (2500 h), outperforming all previously reported neutral catalysts and rivaling conventional alkaline systems. In particular, practical ampere-scale zinc-air batteries (ZABs) stack are constructed with a capacity of 5.93 Ah and can stably operate under 1.0 A and 1.0 Ah conditions, demonstrating broad application prospects. This work provides a novel and feasible perspective for designing neutral oxygen electrocatalysts and reveals the future commercial potential in mobile power supply and large-scale energy storage.

Interfacial Water Orientation in Neutral Oxygen Catalysis for Reversible Ampere‐scale Zinc‐air Batteries

The neutral oxygen catalysis is an electrochemical reaction of the utmost importance in energy generation, storage application, and chemical synthesis. However, the restricted availability of protons poses a challenge to achieving kinetically favorable oxygen catalytic reactions. Here, we alter the interfacial water orientation by adjusting the Brønsted acidity at the catalyst surface, to break the proton transfer limitation of neutral oxygen electrocatalysis. An unexpected role of water molecules in improving the activity of neutral oxygen catalysis is revealed, namely, increasing the H‐down configuration water in electric double layers rather than merely affecting the energy barriers for reaction limiting steps. The proposed porous nanofibers with atomically dispersed MnN3 exhibit record‐breaking activity (EORR@1/2/EOER@10 mA = 0.85/1.65 V vs. RHE) and reversibility (2500 h), outperforming all previously reported neutral catalysts and rivaling conventional alkaline systems. In particular, practical ampere‐scale zinc‐air batteries (ZABs) stack are constructed with a capacity of 5.93 Ah and can stably operate under 1.0 A and 1.0 Ah conditions, demonstrating broad application prospects. This work provides a novel and feasible perspective for designing neutral oxygen electrocatalysts and reveals the future commercial potential in mobile power supply and large‐scale energy storage.

Synergistic physical and chemical effects of MOF-derived porous Fe3C–NC to boost the performance of Li–S batteries

Lithium–sulfur (Li–S) batteries are one of the key objects of next-generation energy storage systems due to their high energy density and low-cost characteristics. However, the slow reaction kinetics and serious shuttle effect of lithium polysulfides (LiPSs) have hindered their practical application. In this work, metal-organic framework-derived Fe3C decorated nitrogen-doped carbon matrix (Fe3C–NC) composites were prepared to modify the separator to promote the reaction kinetics of Li–S batteries. The porous and conductive NC facilitates the trapping of LiPSs, rapid transfer of charge, and alleviated volume expansion, while the Fe3C–NC with optimum Fe3C content can significantly reduce the energy barrier of the electrochemical conversion reaction, accelerate the transport of lithium ions, and enhance the reaction kinetics of LiPSs, which are conducive to inhibit the shuttle effect through synergistic physical and chemical interactions. The Li–S battery with Fe3C–NC separator exhibits excellent cycle stability with an initial discharge specific capacity of 1099.19 mAh g−1 at 1 C and a low-capacity decay of 0.068% per cycle over 500 cycles. Even at a high S loading of 5.93 mg cm−2, it still delivers reliable cyclic stability with an initial discharge specific capacity of 903.65 mAh g−1 at 0.1 C. This work provides a convenient and effective method for the application of metallic materials combined with nitrogen-doped carbon matrix in high-performance Li–S batteries.

Enhancing the Built-in Electric Field in Oxygen Vacancies-Enriched I-Doped Bi3O4Cl for Visible Light-Driven Photocatalytic Oxidation.

In semiconductor catalysts, rational doping of nonmetallic elements holds significant scientific and technological importance for enhancing photocatalytic performance. Here, using a one-step hydrothermal technique, we synthesized iodine-doped Bi3O4Cl composite and evaluated the impact of iodine doping on its photocatalytic capability for organic dye degradation under visible light irradiation. In this study, we demonstrate that the introduction of iodide ions not only provides an ideal built-in electric field (BIEF) for Bi3O4Cl but also induces the generation of additional oxygen vacancies (OVs). The significantly enhanced BIEF, along with the collaborative effect of the OVs-induced narrow bandgap in Bi3O4Cl, effectively promotes the separation and transfer efficiency of photogenerated charges while suppressing recombination. Under this driving force, photogenerated electrons transfer to the surface OVs, facilitating the activation of surface oxygen, thereby forming highly active superoxide radicals (•O2). Simultaneously, oxygen vacancy engineering can reduce the reaction energy barrier, thereby facilitating the formation of singlet oxygen (1O2), which contributes significantly to photocatalytic processes. The results indicate that under visible light, the prepared iodine-doped Bi3O4Cl exhibits a 6.5-fold increase in the degradation rate constant for rhodamine B and demonstrates enhanced photocatalytic activity toward methyl orange and methylene blue. This study not only provides strong references for optimizing structural design to enhance photocatalytic performance but also offers profound insights into the synergistic effects of BIEF and OVs on charge transfer mechanisms in photocatalytic systems.

Implications of Pyrolytic Gas Dynamic Evolution on Dissolved Black Carbon Formed During Production of Biochar from Nitrogen-Rich Feedstock.

Gases and dissolved black carbon (DBC) formed during pyrolysis of nitrogen-rich feedstock would affect atmospheric and aquatic environments. Yet, the mechanisms driving biomass gas evolution and DBC formation are poorly understood. Using thermogravimetric-Fourier transform infrared spectrometry and two-dimensional correlation spectroscopy, we correlated the temperature-dependent primary noncondensable gas release sequence (H2O → CO2 → HCN, NH3 → CH4 → CO) with specific defunctionalization stages in the order: dehydration, decarboxylation, denitrogenation, demethylation, and decarbonylation. Our results revealed that proteins in feedstock mainly contributed to gas releases, and low-volatile pyrolytic products contributed to DBC. Combining mass difference analysis with Fourier transform ion cyclotron resonance mass spectrometry, we showed that 44-60% of DBC molecular compositions were correlated with primary gas-releasing reactions. Dehydration (-H2O), with lower reaction energy barrier, contributed to DBC formation most at 350 and 450 °C, whereas decarboxylation (-CO2) and deamidization (-HCNO) prevailed in contributing to DBC formation at 550 °C. The aromaticity changes of DBC products formed via gas emissions were deduced. Compared to their precursors, dehydration increased DBC aromaticity, while deamidization reduced the aromaticity of DBC products. These insights on pyrolytic byproducts help predict and tune DBC properties via changing gas formed during biochar production, minimizing their negative environmental impacts.

Strongly Coupled Interface in Electrostatic Self-Assembly Covalent Triazine Framework/Bi19S27Br3 for High-Efficiency CO2 Photoreduction.

Constructing a strong bonded interface is highly desired to build fast charge-transfer channels and tune reactive sites for optimizing CO2 photoreduction. In this work, a covalent triazine framework (CTF) combined with a Bi19S27Br3 heterojunction is designed using an electrostatic self-assembly process. Due to the oppositely charged states between two components and ultrasonic treatment, a strong coupled interface is realized with the formation of Bi-C/N/O bonds, leading to robust interfacial polarization. This feature causes interfacial charge redistribution, intensifies the interaction between triazine N reactive sites and CO2, stabilizes the intermediate state, and lowers the reaction energy barrier. Meanwhile, the chemically bonded interface favors rapid electron migration from Bi19S27Br3 to CTF, as proved by ultrafast transient absorption spectroscopy and in situ irradiation XPS. As a result, CTF/Bi19S27Br3 delivers a superior CO2 photoreduction performance to yield CO (572.2 μmol g-1 h-1) in a pure water system, which is 38.6 times that of Bi19S27Br3, with apparent quantum yields up to 7.9 and 6.2% at 380 and 400 nm, respectively. This strong interfacial coupling strategy provides an accessible pathway to designing interfacial polarized, high-efficiency photocatalysts.

Chlorine-Doped SnO2 Nanoflowers on Nickel Hollow Fiber for Enhanced CO2 Electroreduction at Ampere-Level Current Densities.

Renewable energy-driven electrochemical CO2 reduction has emerged as a promising technology for a sustainable future. However, achieving efficient production of storable liquid fuels at ampere-level current densities remains a significant hurdle in the large-scale implementation of CO2 electroreduction. Here we report a novel catalytic electrode comprising chlorine-doped SnO2 nanoflowers arrayed on the exterior of three-dimensional nickel hollow fibers. This electrode demonstrates exceptional electrocatalytic performance for converting CO2 to formate, achieving a remarkable formate selectivity of 99 % and a CO2 single-pass conversion rate of 93 % at 2 A cm-2. Furthermore, it exhibits excellent stability, maintaining a formate selectivity of above 94 % for 520 h at a current density of 3 A cm-2. Experimental results combined with theoretical calculations confirm that the enhanced mass transfer facilitated by the hollow fiber penetration effect, coupled with the well-retained Sn4+ species and Sn-Cl bonds, synergistically elevates the activity of CO2 conversion. The incorporation of chlorine into SnO2 enhances electron transport and CO2 adsorption, substantially lowering the reaction energy barrier for the crucial intermediate *OCHO formation, and boosting the formate production.

One-component anti-aging agents.

Polymer photo-oxidation aging is a significant issue in plastics engineering, leading to reduced performance, shorter lifespan, and additional pollution. Anti-aging agents, including antioxidants and ultraviolet (UV)-shielding agents, are used to ameliorate the above problems. However, multi-component agents involve complex synthesis, mixed processing, and environmental concerns. Therefore, developing robust, multi-functional, one-component anti-aging agents is crucial. This study proposed a new class of one-component poly(coumarin) anti-aging agents, synthesized through enzymatic polymerization of coumarin. These agents exhibited a broader UV absorption spectrum and higher antioxidative capacity than commercial UV-shielding agent UV326 and antioxidant AO1010. Calculating the O-H bond dissociation energy and reaction energy barrier with peroxy free radicals (ROO˙) showed that the material could effectively attenuate UV radiation and scavenge free radicals, improving anti-aging properties. Further studies indicated the potential of poly(coumarin) anti-aging agents for enhanced polymer photostability and improved food preservation packaging. Consequently, poly(coumarin) nanoparticles can act as versatile anti-aging compounds, potentially replacing conventional multi-component agents and providing a new foundation for one-component materials with multiple functions.

Thick and dense nitrogen-doped hafnium carbide ultra-high temperature thermal protection coating for outstanding ablation resistance up to 2600 ℃

Transition metal carbon-nitrides, typically represented by HfCN, have become the latest progress among the ultra-high temperature ceramics. In this study, single-phase solid solution HfCN coating was successfully synthesized from spray granulated HfC-HfN composite powder followed by employing the dual solid solution effects of radio frequency inductively coupled plasma spheroidization and supersonic atmospheric plasma spraying processes. The coating was nearly dense (only 2.3% in porosity) with a high thickness of ~ 270 μm. Compared with HfC coating, the HfCN coating exhibited higher hardness and elastic modulus. After plasma ablation at a high heat flux of 8.2MW/m2 for 200s, the HfCN coating exhibited a surface temperature of up to 2600 ℃ and can firmly protect the refractory tungsten substrate from oxidation failure. This outstanding performance illustrates that doping N element in HfC crystal can effectively improve the energy barrier for oxidation reaction and oxygen adsorption compared with typical HfC coating.

Reactivity in Friedel-Crafts aromatic benzylation: the role of the electrophilic reactant.

Density functional theory is employed in understanding the reactivity in the TiCl4 catalyzed Friedel-Crafts benzylation of benzene with substituted benzyl chlorides in nitromethane solvent. A series of ten substituted (in the aromatic ring) benzyl chlorides are characterized by theoretical reactivity indices. The theoretical parameters are juxtaposed to experimental relative rates of benzylation. It is established that the carbon-chlorine ionic bond dissociation energy and the Hirshfeld charge at the chlorine atom for the benzyl chlorides reactants - describe quite satisfactorily the reactivity trends. These results provide further insights into the factors governing reactivity in EAS reactions, which so far have been mostly focused on rate variations induced by changes in the structure of the aromatic substrate. The EAS benzylation investigated is quite unusual since, in contrast to most EAS reactions, the latest experimental kinetic results suggest that the aromatic substrate does not participate in the kinetic equation of the process. To shed more light on this unexpected result, we also conducted a theoretical study on the mechanistic pathway by applying M06-2X density functional computations combined with several basis sets: 6-311+G(d,p), 6-311+G(2df,2p), and def2-TZVPP. Because of the well-known difficulties in evaluating realistic free energy barriers for organic reactions, we tested two solvent models in determining the barrier for the TiCl4-catalyzed Friedel-Crafts benzylation of benzene by benzyl chloride. Since all methods employed did not provide satisfactory results for the free energy barriers, we used a combination of theoretically estimated enthalpy barriers and the available (from kinetic experiments) entropy contribution. This approach enabled us to verify that indeed the rate of this EAS reaction does not depend on the nature of the aromatic substrate. The computations revealed the structure and relative energies of the critical structures along the mechanistic pathway. Four intermediates were established along the reaction route.

Tunable heteroassembly of 2D CoNi LDH and Ti3C2 nanosheets with enhanced electrocatalytic activity for oxygen evolution.

The sluggish kinetics of the oxygen evolution reaction (OER) is the bottleneck to developing hydrogen energy based on water electrolysis, which can be significantly improved using high performance catalysts. In this context, CoNi layered double hydroxide (LDH)/Ti3C2 heterostructures are obtained using electrostatic attraction of the positively charged LDH and negatively charged Ti3C2 nanosheets as the catalyst to optimize the OER performance. Such alternate stacking exhibits good catalytic activity with a lower overpotential and a small Tafel slope, outperforming their individual components. The results of density functional theory (DFT) simulation show that the charge transfers from Ti3C2 to CoNi LDH not only adjust the electron distribution, but also increase the electron density of the interfacial active sites, thus enhancing the electron transfer efficiency inside the heterostructures. Moreover, the cobalt and nickel ions exhibit a synergistic effect in supplying more electrons to adsorb the adjacent intermediates with active hydrogen and oxygen vacancies, to improve the adsorption capability and to reduce the reaction energy barriers. These findings provide a rewarding avenue towards the design of highly efficient electrocatalysts for OER.

Boosting selective chlorine evolution reaction: Impact of Ag doping in RuO2 electrocatalysts.

The chlor-alkali process is critical to the modern chemical industry because of the wide utilization of chlorine gas (Cl2). More than 95% of global Cl2 production relies on electrocatalytic chlorine evolution reaction (CER) through chlor-alkali electrolysis. The RuO2 electrocatalyst serves as the main active component widely used in commercial applications. However, oxygen evolution reaction (OER) generally competes with CER electrocatalysts at RuO2 electrocatalyst owing to the intrinsically scaling reaction energy barrier of *OCl and *OOH intermediates, leading to decreased CER selectivity, high energy consumption, and increased cost. Here, the effect of Ag doping on selective CER over RuO2 electrocatalysts prepared by a sol-gel method has been systematically studied. We found that Ag-doping can effectively improve the Faradaic efficiency of RuO2 electrocatalyst for CER. Furthermore, the improved CER selectivity of Ag-doped RuO2 electrocatalysts is highly dependent on the Ag-doping concentration. The optimized Ag0.15Ru0.85O2 electrocatalyst displays an overpotential of 105mV along with a selectivity of 84.64±1.84% in 5.0M NaCl electrolyte (pH = 2.0±0.05), significantly outperforming undoped one (142mV, 72.75±1.52%). Our experiments and density functional theory (DFT) calculations show electron transfer from Ag+ to Ru4+ suppresses *OOH intermediates desorption on Ag-doped RuO2, enabling improved CER selectivity. Such designs of Ag-doped RuO2 electrocatalysts are expected to be favorable for practical chlor-alkali applications.

Enhanced electrocatalytic nitrate-to-ammonia performance from Mott-Schottky design to induce electron redistribution.

Constructing highly efficient electrocatalysts via interface manipulation and structural design to facilitate rapid electron transfer in electrocatalytic nitrate-to-ammonia conversion is crucial to attaining superior NH3 yield rates. Here, a Mott-Schottky type electrocatalyst of Co/In2O3 with a continuous fiber structure has been designed to boost the electrocatalytic nitrate-to-ammonia performance. The optimized Co/In2O3-1 catalyst exhibits an impressive NH3 yield rate of 70.1 mg cm-2 h-1 at -0.8 V vs. the reversible hydrogen electrode (RHE), along with an NH3 faradaic efficiency (FE) of 93.34% at 0 V vs. RHE, greatly outperforming the single-component Co and In2O3 samples. The yield rate of Co/In2O3-1 is also superior to that of most currently reported Co-based catalysts and heterostructured ones. Evidence from experiments and theoretical results confirms the formation of a Mott-Schottky heterojunction, which achieves a Co site enriched with electrons, coupled with an In2O3 facet enriched with holes, inducing an electron redistribution to promote the utilization of electroactive sites. Consequently, the reaction energy barrier for nitrate-to-ammonia conversion is significantly reduced, further enhancing its yield efficiency.

CoNCNTs anchored with Ru/RuO2 heterojunction nanostructures as an electrocatalyst for highly effective water splitting

CoNCNTs anchoring Ru/RuO2 heterojunction nanostructure can induce Ru site charge density redistribution, balance the hydrolysis dissociation energy and free energy of adsorption of intermediates, thus reducing the reaction energy barrier of HER/OER.

Recent advances in irradiation-mediated synthesis and tailoring of inorganic nanomaterials for photo-/electrocatalysis.

Photo-/electrocatalysis serves as a cornerstone in addressing global energy shortages and environmental pollution, where the development of efficient and stable catalysts is essential yet challenging. Despite extensive efforts, it's still a formidable task to develop catalysts with excellent catalytic behaviours, stability, and low cost. Because of its high precision, favorable controllability and repeatability, radiation technology has emerged as a potent and versatile strategy for the synthesis and modification of nanomaterials. Through meticulous control of irradiation parameters, including energy, fluence and ion species, various inorganic photo-/electrocatalysts can be effectively synthesized with tailored properties. It also enables the efficient adjustment of physicochemical characteristics, such as heteroatom-doping, defect generation, heterostructure construction, micro/nanostructure control, and so on, all of which are beneficial for lowering reaction energy barriers and enhancing energy conversion efficiency. This review comprehensively outlines the principles governing radiation effects on inorganic catalysts, followed by an in-depth discussion of recent advancements in irradiation-enhanced catalysts for various photo-/electrocatalytic applications, such as hydrogen and oxygen evolution reactions, oxygen reduction reactions, and photocatalytic applications. Furthermore, the challenges associated with ionizing and non-ionizing radiation are discussed and potential avenues for future development are outlined. By summarizing and articulating these innovative strategies, we aim to inspire further development of sustainable energy and environmental solutions to drive a greener future.

Enhanced Transformation Kinetics of Polysulfides Enabled by Synergistic Catalysis of Functional Graphitic Carbon Nitride for High‐Performance Li‐S Batteries

AbstractThe introduction of an electrocatalyst to accelerate the kinetics of lithium polysulfides (LiPSs) reduction/oxidation is beneficial to enhance the capacity of sulfur cathode and inhibit the shuttling effect of LiPSs. However, current electrocatalysts mainly focus on the metal‐based active sites to reduce the reaction barriers, and there remains a great challenge in developing light‐weighted metal‐free catalysts. In this work, 1D graphitic carbon nitride nanorods (g‐C3N4‐NRs) with carboxyl (─COOH) and acylamide (─CONH2) functional groups are designed as metal‐free electrocatalysts for lithium‐sulfur batteries to accelerate the transport of Li+ and the conversion of LiPSs. The density functional theory (DFT) calculations prove that the existence of ─COOH group realizes the adsorption of LiPSs and accelerates the transport of Li+, while the ─CONH2 groups reduce the reaction energy barrier of S8 to Li2S. In addition, in situ UV–vis and Li2S nucleation/dissociation experiments also verify that g‐C3N4‐NRs achieve rapid adsorption and transformation of LiPSs under the synergistic action of ─COOH and ─CONH2 functional groups. Consequently, the sulfur cathode based on the g‐C3N4‐NRs‐PP separator remains at a specific capacity of 700.3 mAh g−1 after 70 cycles at 0.2 C, at 0 °C. This work provides a new strategy for breaking through the bottleneck of metal‐free catalysts for high‐performance lithium‐sulfur batteries.