Rational Design of FeNi Bimetal Modified Covalent Organic Frameworks for Photoconversion of Anthropogenic CO2 into Widely Tunable Syngas

Direct photoconversion of low‐concentration CO₂ into a widely tunable syngas (i.e., CO/H₂ mixture) provides a feasible outlet for the high value‐added utilization of anthropogenic CO₂. However, in the low‐concentration CO₂ photoreduction system, it remains a huge challenge to screen appropriate catalysts for efficient CO and H₂ production, respectively, and provide a facile parameter to tune the CO/H₂ ratio in a wide range. Herein, by engineering the metal sites on the covalent organic frameworks matrix, low‐concentration CO₂ can be efficiently photoconverted into tunable syngas, whose CO/H₂ ratio (1:19–9:1) is obviously wider than reported systems. Experiments and density functional theory calculations indicate that Fe sites serve as the H₂ evolution sites due to the much stronger binding affinity to H₂O, while Ni sites act as the CO production sites for the higher affinity to CO₂. Notably, the widely tunable syngas can also be produced over other Fe/Ni‐based bimetal catalysts, regardless of their structures and supporting materials, confirming the significant role of the metal sites in regulating the selectivity of CO₂ photoreduction and providing a modular design strategy for syngas production.     

Reductive Transformation of Layered‐Double‐Hydroxide Nanosheets to Fe‐Based Heterostructures for Efficient Visible‐Light Photocatalytic Hydrogenation of CO

Conversion of syngas (CO, H₂) to hydrocarbons, commonly known as the Fischer–Tropsch (FT) synthesis, represents a fundamental pillar in today's chemical industry and is typically carried out under technically demanding conditions (1–3 MPa, 300–400 °C). Photocatalysis using sunlight offers an alternative and potentially more sustainable approach for the transformation of small molecules (H₂O, CO, CO₂, N₂, etc.) to high‐valuable products, including hydrocarbons. Herein, a novel series of Fe‐based heterostructured photocatalysts (Fe‐x) is successfully fabricated via H₂ reduction of ZnFeAl‐layered double hydroxide (LDH) nanosheets at temperatures (x) in the range 300–650 °C. At a reduction temperature of 500 °C, the heterostructured photocatalyst formed (Fe‐500) consists of Fe⁰ and FeO_x nanoparticles supported by ZnO and amorphous Al₂O₃. Fe‐500 demonstrates remarkable CO hydrogenation performance with very high initial selectivities toward hydrocarbons (89%) and especially light olefins (42%), and a very low selectivity towards CO₂ (11%). The intimate and abundant interfacial contacts between metallic Fe⁰ and FeO_x in the Fe‐500 photocatalyst underpins its outstanding photocatalytic performance. The photocatalytic production of high‐value light olefins with suppressed CO₂ selectivity from CO hydrogenation is demonstrated here.     

Co‐Based Catalysts Derived from Layered‐Double‐Hydroxide Nanosheets for the Photothermal Production of Light Olefins

Solar‐driven Fischer–Tropsch synthesis represents an alternative and potentially low‐cost route for the direct production of light olefins from syngas (CO and H₂). Herein, a series of novel Co‐based photothermal catalysts with different chemical compositions are successfully fabricated by H₂ reduction of ZnCoAl‐layered double‐hydroxide nanosheets at 300–700 °C. Under UV–vis irradiation, the photothermal catalyst prepared at 450 °C demonstrates remarkable CO hydrogenation performance, affording an olefin (C_2–4⁼) selectivity of 36.0% and an olefin/paraffin ratio of 6.1 at a CO conversion of 15.4%. Characterization studies using X‐ray absorption fine structure and high‐resolution transmission electron microscopy reveal that the active catalyst comprises Co and Co₃O₄ nanoparticles on a ZnO–Al₂O₃ mixed metal oxide support. Density functional theory calculations further demonstrate that the oxide‐decorated metallic Co nanoparticle heterostructure weakens the further hydrogenation ability of the corresponding Co, leading to the high selectivity to light olefins. This study demonstrates a novel solar‐driven catalyst platform for the production of light olefins via CO hydrogenation.     

Iron Carbides: Control Synthesis and Catalytic Applications in COx Hydrogenation and Electrochemical HER

Catalytic transformation of CO_x (x = 1, 2) with renewable H₂ into valuable fuels and chemicals provides practical processes to mitigate the worldwide energy crisis. Fe‐based catalytic materials are widely used for those reactions due to their abundance and low cost. Novel iron carbides are particularly promising catalytic materials among the reported ferrous catalysts. Recently, a series of strategies has been developed for the preparation of iron carbide nanoparticles and their nanocomposites. Control synthesis of FeC_x‐based nanomaterials and their catalytic applications in CO_x hydrogenation and electrochemical hydrogen evolution reaction (HER) are reviewed. The discussion is focused on the unique catalytic activities of iron carbides in CO_x hydrogenation and HER and the correlation between structure and catalytic performance. Future synthesis and potential catalytic applications of iron carbides are also summarized.     

Synergistic Catalysis over Iron‐Nitrogen Sites Anchored with Cobalt Phthalocyanine for Efficient CO2 Electroreduction

Simultaneously achieving high Faradaic efficiency, current density, and stability at low overpotentials is essential for industrial applications of electrochemical CO₂ reduction reaction (CO₂RR). However, great challenges still remain in this catalytic process. Herein, a synergistic catalysis strategy is presented to improve CO₂RR performance by anchoring Fe‐N sites with cobalt phthalocyanine (denoted as CoPc©Fe‐N‐C). The potential window of CO Faradaic efficiency above 90% is significantly broadened from 0.18 V over Fe‐N‐C alone to 0.71 V over CoPc©Fe‐N‐C while the onset potential of CO₂RR over both catalysts is as low as ?0.13 V versus reversible hydrogen electrode. What is more, the maximum CO current density is increased ten times with significantly enhanced stability. Density functional theory calculations suggest that anchored cobalt phthalocyanine promotes the CO desorption and suppresses the competitive hydrogen evolution reaction over Fe‐N sites, while the *COOH formation remains almost unchanged, thus demonstrating unprecedented synergistic effect toward CO₂RR.     

Highly Efficient Carbon Dioxide Hydrogenation to Methanol Catalyzed by Zigzag Platinum–Cobalt Nanowires

Carbon dioxide (CO₂) hydrogenation is an effective strategy for CO₂ utilization, while unsatisfied conversion efficiencies remain great challenges. It is reported herein that zigzag Pt–Co nanowires (NWs) with Pt‐rich surfaces and abundant steps/edges can perform as highly active and stable CO₂ hydrogenation catalysts. It is found that tuning the Pt/Co ratio of the Pt–Co NWs, solvents, and catalyst supports could well optimize the CO₂ hydrogenation to methanol (CH₃OH) with the Pt₄Co NWs/C exhibiting the best performance, outperforming all the previous catalysts. They are also very durable with limited activity decays after six catalytic cycles. The diffuse reflectance infrared Fourier transform spectroscopy result of CO₂ adsorption shows that the Pt₄Co NWs/C undergoes the adsorption/activation of CO₂ by forming appropriate carboxylate intermediates, and thus enhancing the CH₃OH production.     

Oxalate-Assisted Synthesis of Hollow Carbon Nanocage With Fe Single Atoms for Electrochemical CO2 Reduction

Metal single-atom catalysts are promising in electrochemical CO₂ reduction reaction (CO₂RR). The pores and cavities of the supports can promote the exposure of active sites and mass transfer of reactants, hence improve their performance. Here, iron oxalate is added to ZIF-8 and subsequently form hollow carbon nanocages during calcination. The formation mechanism of the hollow structure is studied in depth by controlling variables during synthesis. Kirkendall effect is the main reason for the formation of hollow porous carbon nanocages. The hollow porous carbon nanocages with Fe single atoms exhibit better CO₂RR activity and CO selectivity. The diffusion of CO₂ facilitated by the mesoporous structure of carbon nanocage results in their superior activity and selectivity. This work has raised an effective strategy for the synthesis of hollow carbon nanomaterials, and provides a feasible pathway for the rational design of electrocatalysts for small molecule activation.     

Single-atom catalysts with bimetallic centers for high-performance electrochemical CO2 reduction

The electrochemical CO₂ reduction reaction (CO₂RR) is a promising approach to alleviating global warming while concomitantly producing synthesis gas. Simultaneously achieving high current densities and tunable CO/H₂ (syngas) ratios remains a highly desired yet difficult challenge. Herein, we developed a 3D carbon-based material exhibiting bimetallic centers (NiNC and FeNC) with synergistic effects for the CO₂RR. The molar CO/H₂ ratio (∼1:3 to ∼4:1) was altered by varying the configuration structures of the metal-N sites and tuning the applied potential for industrial applications of syngas. Density functional theory calculations verified these experimental results. Additionally, varying the configuration structures of bimetallic centers changed the rate-limiting steps of FePc@NiNC(+0.95 eV), NiNC/FeNC (+1.25 eV) and NiPc@FeNC (+1.37 eV) for CO₂RR, while maintaining high catalytic activity with tunable syngas production. The reported materials system in this work represents a significant advancement of the CO₂RR towards practical applications.     

Moving Frontiers in Transition Metal Catalysis: Synthesis,Characterization and Modeling

Nanosized transition metal particles are important materials in catalysis with a key role not only in academic research but also in many processes with industrial and societal relevance. Although small improvements in catalytic properties can lead to significant economic and environmental impacts, it is only now that knowledge‐based design of such materials is emerging, partly because the understanding of catalytic mechanisms on nanoparticle surfaces is increasingly improving. A knowledge‐based design requires bottom‐up synthesis of well‐defined model catalysts, an understanding of the catalytic nanomaterials “at work” (operando), and both a detailed understanding and a prediction by theoretical methods. This article reports on progress in colloidal synthesis of transition metal nanoparticles for preparation of model catalysts to close the materials gap between the discoveries of fundamental surface science and industrial application. The transition metal particles, however, often undergo extensive transformations when applied to the catalytic process and much progress has recently been achieved operando characterization techniques under relevant reaction conditions. They allow better understanding of size/structure–activity correlations in these systems. Moreover, the growth of computing power and the improvement of theoretical methods uncover mechanisms on nanoparticles and have recently predicted highly active particles for CO/CO₂ hydrogenation or direct H₂O₂ synthesis.     

Surface Immobilization of Transition Metal Ions on Nitrogen‐Doped Graphene Realizing High‐Efficient and Selective CO2 Reduction

Electrochemical conversion of CO₂ to value‐added chemicals using renewable electricity provides a promising way to mitigate both global warming and the energy crisis. Here, a facile ion‐adsorption strategy is reported to construct highly active graphene‐based catalysts for CO₂ reduction to CO. The isolated transition metal cyclam‐like moieties formed upon ion adsorption are found to contribute to the observed improvements. Free from the conventional harsh pyrolysis and acid‐leaching procedures, this solution‐chemistry strategy is easy to scale up and of general applicability, thus paving a rational avenue for the design of high‐efficiency catalysts for CO₂ reduction and beyond.     

Electroreduction of Carbon Dioxide Driven by the Intrinsic Defects in the Carbon Plane of a Single Fe–N4 Site

Manipulating the in‐plane defects of metal–nitrogen–carbon catalysts to regulate the electroreduction reaction of CO₂ (CO₂RR) remains a challenging task. Here, it is demonstrated that the activity of the intrinsic carbon defects can be dramatically improved through coupling with single‐atom Fe–N₄ sites. The resulting catalyst delivers a maximum CO Faradaic efficiency of 90% and a CO partial current density of 33 mA cm^?2 in 0.1 m KHCO_3. The remarkable enhancements are maintained in concentrated electrolyte, endowing a rechargeable Zn–CO₂ battery with a high CO selectivity of 86.5% at 5 mA cm^?2. Further analysis suggests that the intrinsic defect is the active sites for CO₂RR, instead of the Fe–N₄ center. Density functional theory calculations reveal that the Fe–N₄ coupled intrinsic defect exhibits a reduced energy barrier for CO₂RR and suppresses the hydrogen evolution activity. The high intrinsic activity, coupled with fast electron‐transfer capability and abundant exposed active sites, induces excellent electrocatalytic performance.     

Well‐Defined Single‐Atom Cobalt Catalyst for Electrocatalytic Flue Gas CO2 Reduction

Single‐atom Co catalyst Co‐Tpy‐C with well‐defined sites is synthesized by pyrolysis of a Co terpyridine (Tpy) organometallic complex. The Co‐Tpy‐C catalyst exhibits excellent activity for the electrochemical CO₂ reduction reaction in aqueous electrolyte, with CO faradaic efficiency (FE) of over 95% from ?0.7 to ?1.0 V (vs RHE). By comparison, catalysts without Co or Tpy ligand added do not show any high CO FE. When simulated flue gas with 15% of CO₂ is used as the source of CO₂, CO FE is kept at 90.1% at ?0.5 V versus RHE. During gas phase flow electrolysis using simulated flue gas, the CO partial current density is further increased to 86.4 mA cm^?2 and CO FE reached >90% at the cell voltage of 3.4 V. Experiments and density functional theory calculations indicate that uniform single‐atom Co–N₄ sites mainly contribute to the high activity for CO₂ reduction.     

Sustainable Hydrothermal Carbonization Synthesis of Iron/Nitrogen‐Doped Carbon Nanofiber Aerogels as Electrocatalysts for Oxygen Reduction

It is urgent to develop new kinds of low‐cost and high‐performance nonprecious metal (NPM) catalysts as alternatives to Pt‐based catalysts for oxygen reduction reaction (ORR) in fuel cells and metal–air batteries, which have been proved to be efficient to meet the challenge of increase of global energy demand and CO₂ emissions. Here, an economical and sustainable method is developed for the synthesis of Fe, N codoped carbon nanofibers (Fe–N/CNFs) aerogels as efficient NPM catalysts for ORR via a mild template‐directed hydrothermal carbonization (HTC) process, where cost‐effective biomass‐derived d (+)‐glucosamine hydrochloride and ferrous gluconate are used as precursors and recyclable ultrathin tellurium nanowires are used as templates. The prepared Fe/N‐CNFs catalysts display outstanding ORR activity, i.e., onset potential of 0.88 V and half‐wave potential of 0.78 V versus reversible hydrogen electrode in an alkaline medium, which is highly comparable to that of commercial Pt/C (20 wt% Pt) catalyst. Furthermore, the Fe/N‐CNFs catalysts exhibit superior long‐term stability and better tolerance to the methanol crossover effect than the Pt/C catalyst in both alkaline and acidic electrolytes. This work suggests the great promise of developing new families of NPM ORR catalysts by the economical and sustainable HTC process.     

Highly Efficient Electroreduction of CO2 on Nickel Single‐Atom Catalysts: Atom Trapping and Nitrogen Anchoring

Construction of single atom catalysts (SACs) with high activity toward electroreduction of CO₂ still remains a great challenge. A very simple and truly cost‐effective synthetic strategy is proposed to prepare SACs via a impregnation–pyrolysis method, through one‐step pyrolysis of graphene oxide aerogel. Compared with other traditional methods, this process is fast and free of repeated acid etching, and thus it has great potential for facile operation and large‐scale manufacturing. Both X‐ray absorption fine structure and high‐angle annular dark‐field scanning transmission electron microscopy images confirm the presence of isolated nickel atoms, with a high Ni loading of ≈2.6 wt%. The obtained 3D porous Ni‐ and N‐codoped graphene aerogel exhibits excellent activity toward electroreduction of CO₂ to CO, in particular exhibiting a remarkable CO Faradaic efficiency of 90.2%. Density functional theory calculations reveal that free energies for the formation of intermediate *COOH on coordinatively unsaturated Ni? N sites are significantly lower than that on Ni? N₄ site, suggesting the outstanding activities of CO₂ electroreduction originate from coordinatively unsaturated Ni? N sites in catalysts.     

Alumina‐Supported CoFe Alloy Catalysts Derived from Layered‐Double‐Hydroxide Nanosheets for Efficient Photothermal CO2 Hydrogenation to Hydrocarbons

A series of novel CoFe‐based catalysts are successfully fabricated by hydrogen reduction of CoFeAl layered‐double‐hydroxide (LDH) nanosheets at 300–700 °C. The chemical composition and morphology of the reaction products (denoted herein as CoFe‐x) are highly dependent on the reduction temperature (x). CO₂ hydrogenation experiments are conducted on the CoFe‐x catalysts under UV–vis excitation. With increasing LDH‐nanosheet reduction temperature, the CoFe‐x catalysts show a progressive selectivity shift from CO to CH₄, and eventually to high‐value hydrocarbons (C₂₊). CoFe‐650 shows remarkable selectivity toward hydrocarbons (60% CH₄, 35% C₂₊). X‐ray absorption fine structure, high‐resolution transmission electron microscopy, Mössbauer spectroscopy, and density functional theory calculations demonstrate that alumina‐supported CoFe‐alloy nanoparticles are responsible for the high selectivity of CoFe‐650 for C₂₊ hydrocarbons, also allowing exploitation of photothermal effects. This study demonstrates a vibrant new catalyst platform for harnessing clean, abundant solar‐energy to produce valuable chemicals and fuels from CO₂.     

Effects of Potassium and Manganese Promoters on Nitrogen-Doped Carbon Nanotube-Supported Iron Catalysts for CO2 Hydrogenation

Nitrogen-doped carbon nanotubes (NCNTs) were used as a support for iron (Fe) nanoparticles applied in carbon dioxide (CO₂) hydrogenation at 633 K and 25 bar (1 bar = 10⁵ Pa). The Fe/NCNT catalyst promoted with both potassium (K) and manganese (Mn) showed high performance in CO₂ hydrogenation, reaching 34.9% conversion with a gas hourly space velocity (GHSV) of 3.1 L·(g·h)⁻¹. Product selectivities were high for olefin products and low for short-chain alkanes for the K-promoted catalysts. When Fe/NCNT catalyst was promoted with both K and Mn, the catalytic activity was stable for 60 h of reaction time. The structural effect of the Mn promoter was demonstrated by X-ray diffraction (XRD), temperature-programmed reduction (TPR) with molecular hydrogen (H₂), and in situ X-ray absorption near-edge structure (XANES) analysis. The Mn promoter stabilized wüstite (FeO) as an intermediate and lowered the TPR onset temperature. Catalytic ammonia (NH₃) decomposition was used as an additional probe reaction for characterizing the promoter effects. The Fe/NCNT catalyst promoted with both K and Mn had the highest catalytic activity, and the Mn-promoted Fe/NCNT catalysts had the highest thermal stability under reducing conditions.     

Optimal mixing method of ZnZrOx and MOR-type zeolite to prepare a bifunctional catalyst for CO2 hydrogenation to lower olefins

In recent years, the issue of global warming caused by CO₂ emissions has become a critical problem and poses a worldwide challenge. To address this issue, we have developed a bifunctional catalyst that can convert CO₂ to lower olefins in a single stage. Our bifunctional catalysts are a combination of two catalysts, a CO₂-to-methanol hydrogenation catalyst (Zn-doped ZrO₂, named ZnZrO_x) and a methanol-to-olefin catalyst (MOR-type zeolite, named MOR104). In this research, we examined the impact of various mixing modes of the two catalysts on product distribution. We tested four different mixing modes using a down-flow fixed bed reactor: (a) ZnZrO_x in the upper layer and MOR104 in the lower layer, (b) catalysts were mixed randomly after being pelletized separately, (c) MOR104 in the upper layer and ZnZrO_x in the lower layer, and (d) granulated catalyst produced by physically mixing both catalyst powders. Our findings indicated that the best performance was achieved with catalyst (d), where the two catalysts were mixed in close proximity. This proximity resulted in efficient supply of methanol produced on ZnZrO_x to MOR104. In other words, the MTO reaction in MOR104 efficiently consumed methanol molecules produced via equilibrium-limited CO₂-to-methanol hydrogenation. When ZnZrO_x and MOR104 were thoroughly mixed, the conversion of CO₂ to methanol shifted towards the product side, resulting in a greater overall utilization of CO₂. Furthermore, the bifunctional catalyst we developed was stable for six hours. Since there have been few studies of bifunctional catalysts containing zeolites other than ZSM-5 and SAPO-34, this study opens up new opportunities for bifunctional catalysts specialized for one-pass hydrocarbon synthesis through CO₂ hydrogenation.     

Cu/ZnO Catalysts Derived from Bimetallic Metal–Organic Framework for Dimethyl Ether Synthesis from Syngas with Enhanced Selectivity and Stability

Direct conversion of syngas to dimethyl ether (DME) through the intermediate of methanol allows more efficient DME production in a simpler reactor design relative to the conventional indirect route. Although Cu/ZnO‐based multicomponent catalysts are highly active for methanol synthesis in this process, the sintering issue of Cu during the prolonged reaction generally deteriorates their performance. In this work, Cu/ZnO catalysts in a novel octahedron structure are prepared by a two‐step pyrolysis of Zn‐doped Cu‐BTC metal–organic framework (MOF) in N₂ and air. The catalyst CZ‐350/A, hybrid of MOF‐derived Cu/ZnO sample CZ‐350 and γ‐Al₂O₃ for methanol dehydration, displays the best activity for DME formation (7.74% CO conversion and 70.05% DME selectivity) with the lowest deterioration rate over 40 h continuous reaction. Such performance is superior to its counterpart CZ‐CP/A made via the conventional coprecipitation method. This is mainly due to the confinement of Cu nanoparticles within the octahedron matrix hindering their migration and aggregation. Besides, partial reduction of ZnO in the activated CZ‐350 prompts the formation of Cu⁺‐O‐Zn, further facilitating the DME production with the highest selectivity compared to literature results. The results clearly indicate that Cu and ZnO distribution in the catalyst architecture plays an important role in DME formation.     

Pd Single‐Atom Catalysts on Nitrogen‐Doped Graphene for the Highly Selective Photothermal Hydrogenation of Acetylene to Ethylene

The selective hydrogenation of acetylene to ethylene in an ethylene‐rich gas stream is an important process in the chemical industry. Pd‐based catalysts are widely used in this reaction due to their excellent hydrogenation activity, though their selectivity for acetylene hydrogenation and durability need improvement. Herein, the successful synthesis of atomically dispersed Pd single‐atom catalysts on nitrogen‐doped graphene (Pd₁/N‐graphene) by a freeze‐drying‐assisted method is reported. The Pd₁/N‐graphene catalyst exhibits outstanding activity and selectivity for the hydrogenation of C₂H₂ with H₂ in the presence of excess C₂H₄ under photothermal heating (UV and visible‐light irradiation from a Xe lamp), achieving 99% conversion of acetylene and 93.5% selectivity to ethylene at 125 °C. This remarkable catalytic performance is attributed to the high concentration of Pd active sites on the catalyst surface and the weak adsorption energy of ethylene on isolated Pd atoms, which prevents C₂H₄ hydrogenation. Importantly, the Pd₁/N‐graphene catalyst exhibits excellent durability at the optimal reaction temperature of 125 °C, which is explained by the strong local coordination of Pd atoms by nitrogen atoms, which suppresses the Pd aggregation. The results presented here encourage the wider pursuit of solar‐driven photothermal catalyst systems based on single‐atom active sites for selective hydrogenation reactions.     

Hybridization of Defective Tin Disulfide Nanosheets and Silver Nanowires Enables Efficient Electrochemical Reduction of CO2 into Formate and Syngas

Integrating the defect engineering and conductivity promotion represents a promising way to improve the performance of CO₂ electrochemical reduction. Herein, the hybridized composite of defective SnS₂ nanosheets and Ag nanowires is developed as an efficient catalyst for the production of formate and syngas toward CO₂ electrochemical reduction. The Schottky barrier in Ag‐SnS₂ hybrid nanosheets is negligible due to the similar Fermi level of SnS₂ nanosheets and Ag nanowires. Accordingly, the free electrons of Ag nanowires participate in the electronic transport of SnS₂ nanosheets, and thus give rise to a 5.5‐fold larger carrier density of Ag‐SnS₂ hybrid nanosheets than that of SnS₂ nanosheets. In CO₂ electrochemical reduction, the Ag‐SnS₂ hybrid nanosheets display 38.8 mA cm^?2 of geometrical current density at –1.0 V vs reversible hydrogen electrode, including 23.3 mA cm^?2 for formate and 15.5 mA cm^?2 for syngas with the CO/H₂ ratio of 1:1. A mechanistic study reveals that the abundant defect sites and carrier density not only promote the conductivity of the electrocatalyst, but also increase the binding strength for CO₂, which account for the efficient CO₂ reduction.