N-doped Carbon Matrix Research Articles

N-doped carbon decorated by Cu3P nanoparticle derived from Aspartic acid - Cu MOF as suitable catalysts for oxygen and hydrogen evolution reactions

The preparation of high-efficiency electrocatalysts for the oxygen and hydrogen evolution process (OER and HER) using an easy, green, and facile preparation method is crucial for the effective and economical use of clean energy sources. We report here an eco-friendly phytic acid (PA)-assisted phosphidation strategy to synthesize a novel Cu3P decorated on N-doped carbon (Cu3P-NC). Its synthesis involves precipitation of rode-like microstructured Cu-based aspartic acid frameworks (Asp-Cu MOF), chemical etching of Asp-Cu MOF to form PA cross-linked Cu complexes, and a final pyrolysis step to get Cu3P-NC with abundant Cu3P nanoparticles loaded on N-doped carbon matrix. The Cu3P-NC catalyst demonstrates catalytic performances with low overpotentials of 116 and 310 mV at 10 mA cm−2, small Tafel slopes of 61.2 and 69.2 mV dec−1, for HER and OER respectively, and high catalytic durability in 1 M KOH. The as-prepared Cu3P-NC electrocatalyst offers a new viewpoint on developing multi-functional electrocatalysts in the water-splitting process using environment-friendly substances such as amino acids.

Metal-organic framework-derived in situ-grown Cu2Sb@NC octahedra for high-performance stable lithium/sodium storage

Intermetallic compounds are considered a special class of alloy-type anode materials that show great potential for use in lithium/sodium-ion batteries due to their inherent advantages, such as high specific capacity and enhanced safety features. However, their practical application is often impeded by the substantial volume changes that occur during the insertion and extraction of Li+/Na+ ions, leading to capacity decay and reduced service life. To address this challenge, we developed a novel composite material comprising Cu2Sb nanoparticles encapsulated within a N-doped octahedral carbon matrix (Cu2Sb@N-C). This composite structure features a heteroatom-doped conductive network, a three-dimensional carbon framework, and finely dispersed Cu2Sb nanoparticles. Benefiting from the heteroatom-doped conductive network, three-dimensional carbon framework and ultrafine Cu2Sb nanoparticles, they not only provide a penetrating network for the fast transfer of charge carriers and improve the accessibility of ions, but also alleviate the agglomeration and volume expansion of Cu2Sb during cycling. For LIBs, the material exhibited a reversible capacity of 1001.0 mAh/g after 330 cycles at 0.2 A/g, while maintaining a substantial capacity of 565.5 mAh/g after 1000 cycles at 1.0 A/g. In the case of SIBs, the material exhibited a capacity of 375.6 mAh/g after 100 cycles at 0.2 A/g. Post-cycling electrode analyses revealed that the Cu2Sb@N-C anode material retained its structural integrity, demonstrating its ability to withstand the continuous insertion and extraction of Li+/Na+ ions. This research contributes insights into the effective design of innovative high-capacity alloy-based anode materials for advanced secondary batteries.

A Photo-Assisted Zinc-Air Battery with MoS2/Oxygen Vacancies Rich TiO2 Heterojunction Photocathode.

Converting solar energy into electrochemical energy is a sustainable strategy, but the design of photo-assisted zinc-air battery (ZAB) with efficient utilization of sunlight faces huge challenges. Herein, a photo-assisted ZAB of a three-electrode system using MoS2/oxygen vacancies-rich TiO2 heterojunction as charge cathode and Fe, N-doped carbon matrix (FeNC) as discharge cathode is constructed, where MoS2 is chosen as solar light-responsive catalytic material and TiO2 acts as electron transport layer and hole blocking layer, arising from a train of thought for efficient charging under sunlight irradiation and light-independent discharging. The introduction of oxygen vacancies in TiO2 facilitates the temporary trapping of carriers and triggers rapid carrier transfer at the interface of the heterojunction, which hinders the recombination of photogenerated holes, thereby facilitating their further participation in the oxygen evolution reaction. Moreover, FeNC exhibits superior oxygen reduction reaction performance due to strong d-π interactions. As a result, the well-built ZABs deliver a low charge voltage (0.71 V) under illumination at 0.1 mA cm-2, and a high power density (167.6mW cm-2) in dark. This work paves a special way for the development of ZABs by directly harvesting solar energy in charging and efficiently discharging regardless of lighting conditions.

Mechanism regulation over dual-atom catalyst enables high-performance oxidative alcohol esterification

The development of heterogeneous catalysts with well-defined uniform isolated or multiple active sites is of great importance for understanding catalytic performances and studying reaction mechanisms. Herein, we present a CoCu dual-atom catalyst (CoCu-DAC) where bonded Co–Cu dual-atom sites are embedded in N-doped carbon matrix with a well-defined Co(OH)CuN6 structure. The CoCu-DAC exhibits higher catalytic activity and selectivity than the Co single-atom catalyst (Co-SAC) and Cu single-atom catalyst (Cu-SAC) counterparts in the catalytic oxidative esterification of alcohols and a variety of methyl and alkyl esters have been successfully synthesized. Kinetic studies reveal that the activation energy (29.7 kJ mol−1) over CoCu-DAC is much lower than that over Co-SAC (38.4 kJ mol−1) and density functional theory (DFT) studies disclose that two different mechanisms are regulated over CoCu-DAC and Co-SAC/Cu-SAC in three-step esterification of alcohols. The bonded Co–Cu and adjacent N species efficiently catalyze the elementary reactions of alcohol dehydrogenation, O2 activation and ester formation, respectively. The stepwise alkoxy pathway (O–H and C–H scissions) is preferred for both alcohol dehydrogenation and ester formation over CoCu-DAC, while the progressive hydroxylalkyl pathway (C–H and O–H scissions) for alcohol dehydrogenation and simultaneous hemiacetal dehydrogenation are favored over Co-SAC and Cu-SAC. Characteristic peaks in the Fourier transform infrared spectroscopy analysis may confirm the formation of the metal-C intermediate and the hydroxylalkyl pathway over Co-SAC.

P-doped RuSe2 on Porous N-Doped Carbon Matrix as Catalysts for Accelerated Sulfur Redox Reactions.

Monocomponent catalysts exhibit the limited catalytic conversion of polysulfides due to their intrinsic electronic structure, but their catalytic activity can be improved by introducing heteroatoms to regulate its electronic structure. However, the rational selection principles of doping elements remain unclear. Here, we are guided by theoretical calculations to select the suitable doping elements based on the balanced relationship between the adsorption strength of lithium polysulfides (LiPSs) and catalytic activity of lithium sulfide. We apply the screening method to develop a new catalyst of phosphorus doped RuSe2, manifesting the further enhanced conductivity compared with original RuSe2, facilitating charge transfer and further modulating the d-band center of RuSe2, thereby augmenting its effectiveness in interacting with LiPSs. Consequently, the assembled cell exhibits an areal capacity of 7.7 mAh cm-2, even under high sulfur loading of 8.0 mg cm-2 and a lean electrolyte condition (5.0 μL mg-1). This rational screening strategy offers a robust solution for the design of advanced catalysts in the field of lithium-sulfur batteries and potentially other domains as well.

Encapsulating Si nanoparticles in ZIF-8-derived carbon through surface amination for stable lithium storage

The application of silicon in lithium-ion batteries has been impaired by the low conductivity and large volume expansion. Herein, we develop a facile “surface amination” strategy to successfully encapsulate Si nanoparticles within the ZIF-8-derived N-doped carbon matrix. The amino group-containing organosilica serves as the linking agent between Si nanoparticles and Zn2+ and facilitates the coating of the ZIF-8 layer on the Si nanoparticles. This in turn induces the construction of N-doped carbon matrix encapsulated Si nanoparticles (NH2-Si@C) during the subsequent carbonization. With buffered volume change and increased conductivity, the rationally designed NH2-Si@C demonstrates a high reversible capacity (1494 mAh g–1 at 1 A g–1) and satisfactory rate performance (1062 mAh g–1 at 5 A g–1).

Anchoring Metal-Nitrogen Sites on Porous Carbon Polyhedra with Highly Accessible Multichannels for Efficient Oxygen Reduction.

Transition metal-nitrogen-carbon complexes, featuring single metal atoms embedded in a nitrogen-doped carbon matrix, emerge as promising alternatives to traditional platinum-based catalysts, offering cost-effectiveness, abundance, and enhanced catalytic performance. This work introduces a novel method for the etching and doping of zeolitic imidazolate frameworks (ZIFs) with transition metals, creating a uniform distribution of secondary metal centers on ZIF surfaces. By disrupting the crystalline symmetry of ZIFs through synthetic defect engineering, we gain access to their entire internal volume, creating multichannel pathways. The absorption of metal ions is theoretically simulated, demonstrating their thermodynamically spontaneous nature. The selective removal of defect channels under Lewis acidic conditions, induced by metal ion alcoholysis/hydrolysis, facilitates the introduction of metal atoms into ZIF cavities. The resulting single-atom catalyst, after pyrolysis, features a three-dimensional (3D) multichannel structure, high surface area, and uniformly dispersed metal atoms within the N-doped carbon matrix, establishing it as an exceptional catalyst for the oxygen reduction reaction (ORR). Our findings highlight the potential of using metal etching in defect-engineered metal-organic frameworks (MOFs) for single-atom catalyst preparation, paving the way for the next generation of high-performance, cost-effective ORR catalysts in sustainable energy systems.

Hybrid Molecular Layer Deposition of Molybdenum-Aminates as Hydrogen Evolution Reaction Electrocatalysts

The development of high-performance hydrogen evolution reaction (HER) electrocatalysts from noble metal-free materials is critical to achieving cost-effective water splitting and ultimately realizing affordable hydrogen based on renewable energy. Compounds based on earth-abundant transition metals have been the subject of great research interest for this purpose, with metal nitrides gaining recent attention due to their high conductivity and corrosion resistance. Molybdenum nitride-based electrocatalysts have shown particular promise, with many of the best reported activities occurring in composite systems wherein crystalline MoNx domains are embedded in an amorphous N-doped carbon matrix. The present work demonstrates the formation of such uniquely active morphologies in films deposited by organic-inorganic hybrid molecular layer deposition (MLD).Hybrid MLD is a hybridization of other well-established layer-by-layer deposition techniques – namely atomic layer deposition (used to deposit inorganic films) and purely organic MLD. This family of techniques involves the cyclical exposure of a growth surface to alternating vapor-phase chemical precursors which react in a self-limiting fashion to saturate available surface sites, offering atomic- and molecular-level control over the resulting films. This presentation will introduce the successful development of hybrid MLD deposition procedures for new Mo-aminate materials using Mo(CO)6 as a Mo precursor and various amine precursors, including ethylenediamine, p-phenylenediamine, and tris(2-aminoethyl)amine.We will describe how the molecular level of control offered by this technique enables tunable variations in film composition and structure, lending unique insights into how the local bonding environment of Mo active sites affects their catalytic properties towards HER. Increased nitrogen loading in the MLD films was shown to decrease the overpotentials required to drive HER in acidic media (0.5 M H2SO4) and improve film stability. Catalysts with N/Mo ratios above 2 demonstrated the best performance, with overpotentials lower than 400 mV at -10 mA/cm2. By incorporating organic components in the MLD films, it was possible to induce desirable morphological changes in the catalytic material – notably including the development of increased active site density – simply through initial exposure to HER testing conditions. The choice of organic precursor affected the rate and extent of these changes through structural effects like crosslinking and crystallinity, which led to more stable catalysts, slowed the rate of morphological changes, and impacted final film structure.

Precise design and construction of NiO-Ni heterostructures for active hydrogen evolution photocatalysis

The design of metal-oxide-metal heterostructure photocatalysts is an effective and widely used approach to solve global environmental problems. In this work, we designed and prepared a NiO-rich NiO-Ni heterostructure in an N-doped carbon matrix as a photocatalyst using a simple chemical method for hydrogen evolution reactions. It has an optimal photocatalytic hydrogen production rate of 1395 μmol. g−1. h−1, which is ∼8 times higher than that of Ni rich NiO-Ni (178 μmol. g−1. h−1). Combined experimental results demonstrate that such a good performance benefits from the specific NiO-Ni interface, which could improve the utilization of sunlight and charge separation efficiency. Moreover, this interface contributes to improved structural stability during the photocatalytic reactions, ensuring superior catalytic performance. This work provides a new strategy for the design and synthesis of efficient precious-metal-free heterostructure catalysts for photocatalytic hydrogen evolution reactions.

Facile synthesis of molybdenum carbide interspersed in biomass-derived N-doped carbon matrix for efficient hydrogen evolution reaction

Facile synthesis of molybdenum carbide interspersed in biomass-derived N-doped carbon matrix for efficient hydrogen evolution reaction

Electrospun MOF-derived N-doped mesoporous carbon fibers embedded with ultrafine vanadium oxide as an ultralong cycling stability for potassium ion storage

Potassium-ion batteries (KIBs) are promising options for large-scale energy storage because of their low cost and low redox potential. The use of anodes with porous structures is an attractive strategy to improve the electrochemical properties of KIBs. However, the development of KIB anodes has been hindered by their low capacity and difficulty in synthesizing porous structures. Herein, ultrafine vanadium oxide nanoparticles embedded in porous N-doped carbon nanofibers (VO@PNCNFs) using electrospinning and one-step heat treatment are reported. The uniform growth of vanadium oxide crystals is facilitated by the porous structure of the carbon nanofiber. The numerous pores play a crucial role in the transfer of electrons and ions and provide structural stability to the N-doped carbon matrix. As a result, the VO@PNCNF electrode demonstrates a high reversible capacity (∼205 mA h g−1 at 1.0 A g−1), good cycle stability over 3000 cycles, and excellent rate performance (95 mA h g−1 at 3.0 A g−1).

Synergistic effect of iron phthalocyanine and ultrafine cobalt nanoparticles for efficient CO2 electroreduction to syngas

Developing efficient electrocatalysts for CO2 electroreduction to syngas with a specific H2/CO ratio over a wide potential window is desperately required but still challenging. In this work, a series of dual-site catalysts composed of iron phthalocyanine (FePc) and ∼18 nm Cobalt nanoparticles (Co NPs) anchored on N-doped carbon matrix has been constructed from zeolitic imidazolate framework-67 (ZIF-67). Benefiting from the synergistic effect of FePc and Co NPs, the derived FePc/Co@N–C catalyst shows impressive capability for CO2 electrolysis to syngas. By varying the pyrolysis temperatures (600–800 °C) of ZIF-67 and the mass ratio of Co@N–C to FePc (1–3), an adjustable H2/CO ratio of 2–4 is obtained, and the value can be maintained stable within a potential window of −0.66 to −0.86 V vs. RHE in an H-type cell. Moreover, this electrocatalyst exhibits favorable stability without distinct performance decay. When conducted in a flow cell, an enhanced catalytic activity is demonstrated with an industrial current density (>100 mA cm−2) at −0.8 V vs. RHE and a steady H2/CO ratio of 2 from −0.4 to −0.6 V vs. RHE. This work provides a promising strategy of designing bifunctional electrocatalysts for syngas generation with stable H2/CO ratio across a wide potential range.

Capillary-driven microchip integrated with nickel phosphide hybrid-modified electrode for the electrochemical detection of glucose

BackgroundTransition metal phosphides with properties similar to platinum metal have received increasing attention for the non-enzymatic detection of glucose. However, the requirement of highly corrosive reagent during sample pretreatment would impose a potential risk to the human body, limiting their practical applications. ResultsIn this study, we report a self-powered microfluidic device for the non-enzymatic detection of glucose using nickel phosphide (Ni2P) hybrid as the catalyst. The Ni2P hybrid is synthesized by pyrolysis of metal-organic framework (MOF)-based precursor and in-situ phosphating process, showing two linear detection ranges (1 μM–1 mM, 1 mM–6 mM) toward glucose with the detection limit of 0.32 μM. The good performance of Ni2P hybrid for glucose is attributed to the synergistic effect of Ni2P active sites and N-doped porous carbon matrix. The microchip is integrated with a NaOH-loaded paper pad and a capillary-based micropump, enabling the automatic NaOH redissolution and delivery of sample solution into the detection chamber. Under the optimized condition, the Ni2P hybrid-based microchip realized the detection of glucose in a user-friendly way. Besides, the feasibility of using this microchip for glucose detection in real serum samples has also been validated. SignificanceThis article presents a facile fabrication method utilizing a MOF template to synthesize a Ni2P hybrid catalyst. By leveraging the synergy between the Ni2P active sites and the N-doped carbon matrix, an exceptional electrochemical detection performance for glucose has been achieved. Additionally, a self-powered chip device has been developed for convenient glucose detection based on the pre-established high pH environment on the chip.

N-doped 3D carbon encapsulating nickel selenide nanoarchitecture with cation defect engineering: An ultrafast and long-life anode for sodium-ion batteries

Transition metal chalcogenides (TMCs) hold great potential for sodium-ion batteries (SIBs) owing to their multielectron conversion reactions, yet face challenges of poor intrinsic conductivity, sluggish diffusion kinetics, severe phase transitions, and structural collapse during cycling. Herein, a self-templating strategy is proposed for the synthesis of a class of metal cobalt-doped NiSe nanoparticles confined within three-dimensional (3D) N-doped macroporous carbon matrix nanohybrids (Co-NiSe/NMC). The cation defect engineering within the developed Co-NiSe and 3D N-doped carbon plays a crucial role in enhancing intrinsic conductivity, reinforcing structural stability, and reducing the barrier to sodium ion diffusion, which are verified by a series of electrochemical kinetic analyses and density functional theory calculations. Significantly, such cation defect engineering not only reduces overpotential but also accelerates conversion reaction kinetics, ensuring both exceptional high-rate capability and extended durability. Consequently, the optimally engineered Co-NiSe/NMC demonstrates a remarkable rate performance, delivering 390 mAh g−1 at 10 A g−1. Moreover, it exhibits an unprecedented lifespan, maintaining a remarkable capacity of 403 mAh g−1 after 1400 cycles and 318 mAh g−1 after 4000 cycles, even at high rates of 1.0 and 2.0 A g−1, respectively. This work marks a substantial advancement in achieving both high performance and prolonged cycle life in sodium-ion batteries.

Fe2O3 nanoparticles anchored on N-doped pinecone-based porous carbon as potential anode for potassium-ion battery

Fe2O3/carbon composites have received widespread attention as a potential anode material for lithium/sodium ion battery owing to its rich reserves, wide distribution, and environmental friendliness. However, studies on potassium-ion battery (PIB) have rarely been reported. Besides, majority carbon-based matrices are mainly focused on the utilization of synthetic carbons, which have a high cost and complicated synthesis process. In contrast, biomass-based carbon is inexpensive, environment-friendly, and abundant in terms of its precursor resources, making it a promising matrix. In this work, the dispersal of Fe2O3 nanoparticles on a N-doped pinecone-based porous carbon matrix (Fe2O3/NPC) was proposed as a simple and effective approach for improving the electrochemical performance of the Fe2O3 anode in potassium-ion battery. Fe2O3/NPC was prepared using a hydrothermal method, and the morphology of Fe2O3 was optimized by varying the reaction temperature. Compared with Fe2O3, NPC and Fe2O3/NPC prepared at different temperature, the Fe2O3/NPC-150 electrode exhibited an improved discharge capacity of 178.7 mAh·g−1 after 100 cycles at 50 mA g−1 with good rate performance and the high capacity retention rate of 91.6 % after 500 cycles. The improved electrochemical performance is attributed to the synergistic effect of small Fe2O3 nanoparticles and N-doped pinecone-based porous carbon. This strategy provides a simple, mild and low cost method for preparing iron based anode materials for potassium-ion battery, and also provides some guidances for large-scale industrial production.

Fast ionic conductor MnSe supported Micron-Si embedded in three-dimensional N-doped carbon matrix for lithium-ion batteries

Silicon is regarded as the most potential anode for the next generation lithium-ion batteries (LIBs) since its superhigh specific capacity and abundant reserves. Nonetheless, the grievous volume variation and inferior connate conductivity imped its further step on the commercial application. Herein, three-dimensional (3D) porous N-doped carbon microspheres, in which silicon is embedded and supported by MnSe, are fabricated via a simple spray drying method, named as MnSe/Si@NC. Such synergy conduces to the weaker polarization phenomenon and lower reactive barrier. Multi kind of electrochemical tests announce that the 3D network supported by MnSe and synthetical chemical bridge bonds, can remarkably ameliorate electron conductivity and structural stability. Benefit from the reasonably designed materials, the MnSe/Si@NC-10 anode expresses an outstanding cycling stability of 1030.8 mAh·g−1 at 2 A g−1 over 1000 cycles and extremely low-capacity loss rate for each cycle with about 0.27 ‰. In a word, this work can provide reference for the designing and preparation of high-performance anode materials utilized in LIBs.

Insights into interfacial catalysis for aqueous reduction of 4-Nitrophenol catalyzed by Ni metal nanoparticles encapsulated within biomass-derived N-doped carbon matrix

As we strive towards a sustainable future in the field of catalysis, it is imperative to draw inspiration from Mother Nature. In this study, we present a straightforward and environmentally friendly approach for the in situ synthesis of nickel metal nanoparticles encapsulated within nitrogen-doped carbon (NNC), derived from daikon biomass. Among the various examined NNC catalysts, NNC-2 characterized by its substantial surface area and high doping content, emerges as the most promising candidate for catalyzing the reduction of 4-nitrophenol. Ab initio molecular dynamics simulations unveil that NNC-2 facilitates a robust Ni-NC interfacial interaction, which stabilizes Ni nanoparticles and supports the exceptional durability and recyclability. Theoretical calculations further elucidate the structure–activity relationship of the catalyst and the mechanistic aspects of the surface reduction of 4-nitrophenol. This insight enhances our understanding of the catalytic processes over carbon-based catalysts, providing a foundation for optimizing catalytic performance and guiding future developments in the field.

Fabricating composites of multicomponent active substances embedded in carbon matrix for enhancing structural stability and redox kinetics of cathode in aqueous zinc-ion batteries

Rechargeable aqueous zinc-ion batteries (ZIBs) are recognized as a potential candidate for large-scale energy storage due to its high-security and low-expense aspects. However, the poor structural stability and sluggish redox kinetics of cathode material lead to the serious capacity fading and bad rate performances, which hinders its practical applications. Herein, a novel one-step pyrolysis strategy is conducted for fabricating the composites of multicomponent active substances (including WO3, Bi and Bi2O3) embedded in amorphous N-doped carbon matrix (BWO@C) using polydopamine-coated Bi2WO6 micro-flowers as the precursors. The amorphous nitrogen-doped carbon endows BWO@C composite to possess more active-sites and higher electrical conductivity for rapid electrons/ions transport, and meanwhile the active substances could be effectively utilized even undergoing thousands of charge/discharge cycles. Therefore, the resulting BWO@C as cathode for aqueous ZIBs exhibits satisfying rate performances as well as outstanding cycling stability. This work provides a simple and efficient pathway for designing the cathode materials with high conductivity and high structural stability to achieve remarkable performances and long life-span of aqueous ZIBs.

Three-dimensional faveolate porous N-doped carbon skeleton embodied with nano Bi toward stable less-Na sodium metal batteries

Sodium metal batteries (SMBs) have been widely investigated recently due to the low price of Na metal, satisfactory energy density and similar chemical properties to lithium. However, SMBs also face challenges like low Na utilization, dendrite growth, dead sodium accumulation, unstable solid electrolyte interphase and massive bubble generation. To improve their safety and cycling stability, herein, we fabricate a porous hybrid framework, i.e., fine Bi nanoparticles anchored in porous N-doped carbon matrix (Bi@PNC), as a modified layer upon Cu collector toward stable SMBs. Upon electrochemical activation, the nanoscale Bi-derived Na–Bi alloy with high sodiophilicity reduces the nucleation overpotential of Na, inhibits the formation of Na dendrites, and decreases the loss of Na during cycling. Thanks to these striking merits, the half cells assembled with Na undergo 1600 cycles (3200 h) at 1 mA cm−2, 1 mAh cm−2 with the average Coulombic efficiency of 99.95%. The optimized Bi@PNC based symmetric cells still maintain the overpotential of ∼9.2 mV under 1 mA cm−2 and depth of discharge of 16.7% after cycling for 2420 h. Furthermore, the assembled less-Na full SMBs exhibit superb electrochemical properties. Our strategy here provides meaningful avenue to construct stable less-Na metallic anodes for advanced SMBs.

Co-ZIF-derived dual Co and Co3S4 nanoparticles encapsulated in N-doped carbon matrix for efficient photocatalytic CO2 reduction

In this study, a novel N-doped carbon-coated dual Co and Co3S4 nanoparticles composite (Co-Co3S4@NC) has been developed by pyrolysis of an ideal flower-like Co-ZIF precursor followed via subsequent hydrothermal sulfidation. Under visible-light irradiation, the Co-Co3S4@NC exhibits outstanding performances for CO2 reduction with H2O vapor into CO (23.14 μmol g−1 h−1) and CH4 (0.62 μmol g−1 h−1) in a continuous flow system, significantly outperforming the single Co@NC photocatalyst. The experimental results demonstrate that the energy band structure in Co-Co3S4@NC can provide a more favorable reduction potential for the effective reduction of CO2. Moreover, the presence of Co3S4 is beneficial for the rapid separation and transfer of charges, thereby enhancing the utilization of photogenerated charge carriers. Thanks to its unique composition, Co-Co3S4@NC possesses abundant active sites for chemisorption and activation of CO2, which facilitates CO2 photoreduction. The reaction mechanism is revealed in detail by analyzing the key intermediate species obtained through in situ DRIFTS. The current work offers a facile route for the construction of MOF-derived composites for promising photocatalytic reactions.