Promoting Electrocatalytic CO2 Reduction to CH4 by Copper Porphyrin with Donor–Acceptor Structures

Molecular catalysts have been receiving increasingly attention in the electrochemical CO₂ reduction reaction (CO₂RR) with attractive features such as precise catalytic sites and tunable ligands. However, the insufficient activity and low selectivity of deep reduction products restrain the utilization of molecular catalysts in CO₂RR. Herein, a donor–acceptor modified Cu porphyrin (CuTAPP) is developed, in which amino groups are linked to donate electrons toward the central CuN₄ site to enhance the CO₂RR activity. The CuTAPP catalyst exhibited an excellent CO₂-to-CH₄ electroreduction performance, including a high CH₄ partial current density of 290.5 mA cm⁻² and a corresponding Faradaic efficiency of 54.8% at –1.63 V versus reversible hydrogen electrode in flow cells. Density functional theory calculations indicated that CuTAPP presented a much lower energy gap in the pathway of producing *CHO than Cu porphyrin without amino group modification. This work suggests a useful strategy of introducing designed donor–acceptor structures into molecular catalysts for enhancing electrochemical CO₂ conversion toward deep reduction products.     

Emerging Carbon‐Based Heterogeneous Catalysts for Electrochemical Reduction of Carbon Dioxide into Value‐Added Chemicals

The electrocatalytic reduction of CO₂ provides a sustainable way to mitigate CO₂ emissions, as well as store intermittent electrical energy into chemicals. However, its slow kinetics and the lack of ability to control the products of the reaction inhibit its industrial applications. In addition, the immature mechanistic understanding of the reduction process makes it difficult to develop a selective, scalable, and stable electrocatalyst. Carbon‐based materials are widely considered as a stable and abundant alternative to metals for catalyzing some of the key electrochemical reactions, including the CO₂ reduction reaction. In this context, recent research advances in the development of heterogeneous nanostructured carbon‐based catalysts for electrochemical reduction of CO₂ are summarized. The leading factors for consideration in carbon‐based catalyst research are discussed by analyzing the main challenges faced by electrochemical reduction of CO₂. Then the emerging metal‐free doped carbon and aromatic N‐heterocycle catalysts for electrochemical reduction of CO₂ with an emphasis on the formation of multicarbon hydrocarbons and oxygenates are discussed. Following that, the recent progress in metal–nitrogen–carbon structures as an extension of carbon‐based catalysts is scrutinized. Finally, an outlook for the future development of catalysts as well as the whole electrochemical system for CO₂ reduction is provided.     

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.     

Hybrid Cu0 and Cux+ as Atomic Interfaces Promote High‐Selectivity Conversion of CO2 to C2H5OH at Low Potential

The mixing of charge states of metal copper catalysts may lead to a much improved reactivity and selectivity toward multicarbon products for CO₂ reduction. Here, an electrocatalyst model composed of copper clusters supported on graphitic carbon nitride (g‐C₃N₄) is proposed; the connecting Cu atoms with g‐C₃N₄ can be oxidized to Cu^{x +} due to substantial charge transfer from Cu to N atoms, while others stay as Cu⁰. It is revealed that CO₂ can be captured and reduced into *CO on the Cu_t⁰ site, owing to its zero oxidation state. More importantly, C–C coupling reaction of two *CHO species on the Cu_t⁰–Cu_b^{x +} atomic interface can occur with a rather low kinetic barrier of 0.57 eV, leading to the formation of the final C₂ product, namely, C₂H₅OH. During the whole process, the limiting potential is just 0.68 V. These findings may open a new avenue for CO₂ reduction into high‐value fuels and chemicals.     

Hydrogen production of nickel–scandia-stabilized zirconia and copper/nickel–scandia-stabilized zirconia catalysts through steam methane reforming for solid oxide fuel cell operation

In this study, the catalytic activities of the steam methane reforming (SMR) reactions with two catalysts, including nickel–scandia-stabilized zirconia (Ni–SSZ) and copper/nickel–scandia-stabilized zirconia (Cu/Ni–SSZ), were examined and compared. The microstructure and crystallinity of the as-prepared catalysts were characterized by scanning electron microscopy, Raman spectroscopy, and X-ray diffraction. Mass spectrometer was applied in the outlet streams, in order to simultaneously monitor the time-dependent kinetics in the reactor for an activity test and conversion examination. Finally, thermogravimetric analysis (TGA) and Raman spectrometer were implemented for further verification of carbon residuals on the catalysts. It was found that the incorporation of Cu on Ni–SSZ imposed significant constraints on the growth of nickel crystallites from NiO during the annealing process in reducing atmospheres. The methane conversion of Ni–SSZ and Cu/Ni–SSZ catalysts (annealed at 300 °C for 2 h) was 36.2 and 26.0%, respectively. However, the amount of carbon residuals on Cu/Ni–SSZ catalyst (300 °C for 2 h) was 18.6%, which is lower than that of the Ni–SSZ catalysts (33.2%) from TGA results. Further Raman experiments revealed that more graphite-like carbon residuals and less defects or amorphous carbons (I_G/I_D?=?2.0) were found in the case of Cu/Ni–SSZ catalysts (300 °C for 2 h). Among the catalysts in this study, the Cu/Ni–SSZ catalyst (300 °C for 2 h) is considered as a promising catalyst for SMR reaction, since it has a fair methane conversion, and characterized higher CO₂ selectivity and lower CO selectivity without compromising the hydrogen purity. More importantly, the least amount of carbon residuals was found in Cu/Ni–SSZ catalyst (300 °C for 2 h), which assured a better lifetime.     

Recent Advances and Perspectives of Core-Shell Nanostructured Materials for Photocatalytic CO2 Reduction

Photocatalytic CO₂ conversion into solar fuels is a promising technology to alleviate CO₂ emissions and energy crises. The development of core-shell structured photocatalysts brings many benefits to the photocatalytic CO₂ reduction process, such as high conversion efficiency, sufficient product selectivity, and endurable catalyst stability. Core-shell nanostructured materials with excellent physicochemical features take an irreplaceable position in the field of photocatalytic CO₂ reduction. In this review, the recent development of core-shell materials applied for photocatalytic reduction of CO_{2 is introduced}. First, the basic principle of photocatalytic CO₂ reduction is introduced. In detail, the classification and synthesis techniques of core-shell catalysts are discussed. Furthermore, it is also emphasized that the excellent properties of the core-shell structure can greatly improve the activity, selectivity, and stability in the process of photocatalytic CO₂ reduction. Hopefully, this paper can provide a favorable reference for the preparation of efficient photocatalysts for CO₂ reduction.     

Recent progress in electrochemical reduction of carbon monoxide toward multi-carbon products

The increasing CO₂ emissions and accompanying climate challenges have boosted the exploration of candidate pathways for storing and utilizing renewable carbon resources. Electrochemical CO₂ reduction (ECO₂R) has been proven as a promising technology for artificial carbon fixation. Nevertheless, the unsatisfactory multi-carbon (C₂₊) product selectivity hinders its widespread use. Recently, the indirect route via electrochemical CO reduction (ECOR) to C₂₊ products has become a potential alternative through the combination with ECO₂R. In this review, we briefly summarize the most recent and instructive research in the ECOR development process from advanced ECOR catalysts and reaction mechanisms. Furthermore, the challenges and outlooks based on current understanding in this field are expounded. These insights and perspectives offer meaningful guidance for grasping ECOR and designing relevant catalysts with enhanced C₂₊ product selectivity.     

Metal‐Free Carbon Materials for CO2 Electrochemical Reduction

The rapid increase of the CO₂ concentration in the Earth's atmosphere has resulted in numerous environmental issues, such as global warming, ocean acidification, melting of the polar ice, rising sea level, and extinction of species. To search for suitable and capable catalytic systems for CO₂ conversion, electrochemical reduction of CO₂ (CO₂RR) holds great promise. Emerging heterogeneous carbon materials have been considered as promising metal‐free electrocatalysts for the CO₂RR, owing to their abundant natural resources, tailorable porous structures, resistance to acids and bases, high‐temperature stability, and environmental friendliness. They exhibit remarkable CO₂RR properties, including catalytic activity, long durability, and high selectivity. Here, various carbon materials (e.g., carbon fibers, carbon nanotubes, graphene, diamond, nanoporous carbon, and graphene dots) with heteroatom doping (e.g., N, S, and B) that can be used as metal‐free catalysts for the CO₂RR are highlighted. Recent advances regarding the identification of active sites for the CO₂RR and the pathway of reduction of CO₂ to the final product are comprehensively reviewed. Additionally, the emerging challenges and some perspectives on the development of heteroatom‐doped carbon materials as metal‐free electrocatalysts for the CO₂RR are included.     

Selective CO2 Electroreduction to Formate on Polypyrrole-Modified Oxygen Vacancy-Rich Bi2O3 Nanosheet Precatalysts by Local Microenvironment Modulation

Challenges remain in the development of highly efficient catalysts for selective electrochemical transformation of carbon dioxide (CO₂) to high-valued hydrocarbons. In this study, oxygen vacancy-rich Bi₂O₃ nanosheets coated with polypyrrole (Bi₂O₃@PPy NSs) are designed and synthesized, as precatalysts for selective electrocatalytic CO₂reduction to formate. Systematic material characterization demonstrated that Bi₂O₃@PPy precatalyst can evolve intoBi₂O₂CO₃@PPy nanosheets with rich oxygen vacancies (Bi₂O₂CO₃@PPy NSs) via electrolyte-mediated conversion and function as the real active catalyst for CO₂ reduction reaction electrocatalysis. Coating catalyst with a PPy shell can modulate the interfacial microenvironment of active sites, which work in coordination with rich oxygen vacancies in Bi₂O₂CO₃ and efficiently mediate directional selective CO₂ reduction toward formate formation. With the fine-tuning of interfacial microenvironment, the optimized Bi₂O₃@PPy-2 NSs derived Bi₂O₂CO₃@PPy-2 NSs exhibit a maximum Faradaic efficiency of 95.8% at −0.8 V (versus. reversible hydrogen electrode) for formate production. This work might shed some light on designing advanced catalysts toward selective electrocatalytic CO₂ reduction through local microenvironment engineering.     

Formation of C?X Bonds in CO2 Chemical Fixation Catalyzed by Metal−Organic Frameworks

Transformation of CO₂ based on metal−organic framework (MOF) catalysts is becoming a hot research topic, not only because it will help to reduce greenhouse gas emission, but also because it will allow for the production of valuable chemicals. In addition, a large number of impressive products have been synthesized by utilizing CO₂. In fact, it is the formation of new covalent bonds between CO₂ and substrate molecules that successfully result in CO₂ solidly inserting into the products, and only four types of new C X bonds, including C H, C C, C N, and C O bonds, are observed in this exploration. An overview of recent progress in constructing C X bonds for CO₂ conversion catalyzed by various MOF catalysts is provided. The catalytic mechanism of generating different C X bonds is further discussed according to both structural features of MOFs and the interactions among CO₂, substrates, as well as MOFs. The future opportunities and challenges in this field are also tentatively covered.     

Effect of additive gases on synthesis of organic compounds from carbon dioxide using non-thermal plasma produced by atmospheric surface discharges

Reduction and recycling of carbon dioxide (CO₂) were performed using a non-thermal plasma produced by a surface discharge at atmospheric pressure. Useful hydrocarbons (CHs) such as dimethyl ether and methane were produced at the discharge voltage of 11 kV, when hydrogen (H₂) gas was mixed with CO₂ and the mixture ratio was 50%. The conversion of CO₂ to the CHs mixing with water vapor of 50% requires a higher discharge voltage of 12 kV. The conversion ratios to the hydrocarbons were several percentage in both H₂ mixture and water vapor mixture cases.     

Electrode Materials Engineering in Electrocatalytic CO2 Reduction: Energy Input and Conversion Efficiency

Electrocatalytic CO₂ reduction (ECR) is a promising technology to simultaneously alleviate CO₂-caused climate hazards and ever-increasing energy demands, as it can utilize CO₂ in the atmosphere to provide the required feedstocks for industrial production and daily life. In recent years, substantial progress in ECR systems has been achieved by the exploitation of various novel electrode materials. The anodic materials and cathodic catalysts that have, respectively, led to high-efficiency energy input and effective heterogenous catalytic conversion in ECR systems are comprehensively reviewed. Based on the differences in the nature of energy sources and the role of materials used at the anode, the fundamentals of ECR systems, including photo-anode-assisted ECR systems and bio-anode-assisted ECR systems, are explained in detail. Additionally, the cathodic reaction mechanisms and pathways of ECR are described along with a discussion of different design strategies for cathode catalysts to enhance conversion efficiency and selectivity. The emerging challenges and some perspective on both anode materials and cathodic catalysts are also outlined for better development of ECR systems.     

Reaction pathways of methanol over Pt/zeolite catalysts: effect of different active sites

The conversion of methanol on Pt-containing zeolites such as KL, NaY, HZSM-5, and H-offretite and on Pt/Al₂O₃ has been investigated over the temperature range 423–723 K in the presence of 59.8 kPa hydrogen. The possibility of directing the process to various pathways (hydrogenation-dehydrogenation, dehydration, and hydrocarbons formation) is discussed. By balancing the activities of the two catalyst components, one can regulate the surface concentrations of the reagents and products as well as the selectivity of the process. It is suggested that under specific conditions the conversion of methanol can be used as a model reaction for preliminary evaluation of the activity of catalysts.     

Morphological and Compositional Design of Pd–Cu Bimetallic Nanocatalysts with Controllable Product Selectivity toward CO2 Electroreduction

Electrochemical conversion of carbon dioxide (electrochemical reduction of carbon dioxide) to value‐added products is a promising way to solve CO₂ emission problems. This paper describes a facile one‐pot approach to synthesize palladium–copper (Pd–Cu) bimetallic catalysts with different structures. Highly efficient performance and tunable product distributions are achieved due to a coordinative function of both enriched low‐coordinated sites and composition effects. The concave rhombic dodecahedral Cu₃Pd (CRD‐Cu₃Pd) decreases the onset potential for methane (CH₄) by 200 mV and shows a sevenfold CH₄ current density at ?1.2 V (vs reversible hydrogen electrode) compared to Cu foil. The flower‐like Pd₃Cu (FL‐Pd₃Cu) exhibits high faradaic efficiency toward CO in a wide potential range from ?0.7 to ?1.3 V, and reaches a fourfold CO current density at ?1.3 V compared to commercial Pd black. Tafel plots and density functional theory calculations suggest that both the introduction of high‐index facets and alloying contribute to the enhanced CH₄ current of CRD‐Cu₃Pd, while the alloy effect is responsible for high CO selectivity of FL‐Pd₃Cu.     

Advanced Catalyst for CO2 Photo-Reduction: From Controllable Product Selectivity by Architecture Engineering to Improving Charge Transfer Using Stabilized Au Clusters

Despite enormous progress and improvement in photocatalytic CO₂ reduction reaction (CO₂RR), the development of photocatalysts that suppress H₂ evolution reaction (HER), during CO₂RR, remains still a challenge. Here, new insight is presented for controllable CO₂RR selectivity by tuning the architecture of the photocatalyst. Au/carbon nitride with planar structure (p Au/CN) showed high activity for HER with 87% selectivity. In contrast, the same composition with a yolk@shell structure (Y@S Au@CN) exhibited high selectivity of carbon products by suppressing the HER to 26% under visible light irradiation. Further improvement for CO₂RR activity was achieved by a surface decoration of the yolk@shell structure with Au₂₅(PET)₁₈ clusters as favorable electron acceptors, resulting in longer charge separation in Au@CN/Au_c Y@S structure. Finally, by covering the structure with graphene layers, the designed catalyst maintained high photostability during light illumination and showed high photocatalytic efficiency. The optimized Au@CN/Au_c/G Y@S structure displays high photocatalytic CO₂RR selectivity of 88%, where the CO and CH₄ generations during 8 h are 494 and 198 µmol/gcat., respectively. This approach combining architecture engineering and composition modification provides a new strategy with improved activity and controllable selectivity toward targeting applications in energy conversion catalysis.     

Tandem catalysis in electrochemical CO2 reduction reaction

Electrochemical CO₂ reduction reaction (CO₂RR) is an attractive pathway for closing the anthropogenic carbon cycle and storing intermittent renewable energy by converting CO₂ to valuable chemicals and fuels. The production of highly reduced carbon compounds beyond CO and formate, such as hydrocarbon and oxygenate products with higher energy density, is particularly desirable for practical applications. However, the productivity towards highly reduced chemicals is typically limited by high overpotential and poor selectivity due to the multiple electron-proton transfer steps. Tandem catalysis, which is extensively utilized by nature for producing biological macromolecules with multiple enzymes via coupled reaction steps, represents a promising strategy for enhancing the CO₂RR performance. Improving the efficiency of CO₂RR via tandem catalysis has recently emerged as an exciting research frontier and achieved significant advances. Here we describe the general principles and also considerations for designing tandem catalysis for CO₂RR. Recent advances in constructing tandem catalysts, mainly including bimetallic alloy nanostructures, bimetallic heterostructures, bimetallic core-shell nanostructures, bimetallic mixture catalysts, metal-metal organic framework (MOF) and metal-metallic complexes, metal-nonmetal hybrid nanomaterials and copper-free hybrid nanomaterials for boosting the CO₂RR performance are systematically summarized. The study of tandem catalysis for CO₂RR is still at the early stage, and future research challenges and opportunities are also discussed.

     

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.     

One-Step Phase Separation for Core-Shell Carbon@Indium Oxide@Bismuth Microspheres with Enhanced Activity for CO2 Electroreduction to Formate

It is a substantial challenge to construct electrocatalysts with high activity, good selectivity, and long-term stability for electrocatalytic reduction of carbon dioxide to formic acid. Herein, bismuth and indium species are innovatively integrated into a uniform heterogeneous spherical structure by a neoteric quasi-microemulsion method, and a novel C@In₂O₃@Bi₅₀ core-shell structure is constructed through a subsequent one-step phase separation strategy due to melting point difference and Kirkendall effect with the nano-limiting effect of the carbon structure. This core-shell C@In₂O₃@Bi₅₀ catalyst can selectively reduce CO₂ to formate with high selectivity (≈90% faradaic efficiency), large partial current density (24.53 mA cm⁻² at −1.36 V), and long-term stability (up to 14.5 h), superior to most of the Bi-based catalysts. The hybrid Bi/In₂O₃ interfaces of core-shell C@In₂O₃@Bi will stabilize the key intermediate HCOO* and suppress CO poisoning, benefiting the CO₂RR selectivity and stability, while the internal cavity of core-shell structure will improve the reaction kinetics because of the large specific surface area and the enhancement of ion shuttle and electron transfer. Furthermore, the nano-limited domain effect of outmost carbon prevent active components from oxidation and agglomeration, helpful for stabilizing the catalyst. This work offers valuable insights into core-shell structure engineering to promote practical CO₂ conversion technology.     

Less-Coordinated Atomic Copper-Dimer Boosted Carbon–Carbon Coupling During Electrochemical CO2 Reduction

This work reports a metal–organic framework (MOF) with less-coordinated copper dimers, which displays excellent electrochemical CO₂ reduction (eCO₂RR) performance with an advantageous current density of 0.9 A cm⁻² and a high Faradaic efficiency of 71% to C₂ products. In comparison with MOF with Cu monomers that are present as Cu₁ O₄ with a coordination number of 3.8 ± 0.2, Cu dimers exist as O₃Cu₁···Cu₂O₂ with a coordination number of 2.8 ± 0.1. In situ characterizations together with theoretical calculations reveal that two *CO intermediates are stably adsorbed on each site of less-coordinated Cu dimers, which favors later dimerization via a key intermediate of *CH₂CHO. The highly unsaturated dual-atomic Cu provides large-quantity and high-quality actives sites for carbon–carbon coupling, achieving the optimal trade-off between activity and selectivity of eCO₂RR to C₂ products.