Research on the Construction Strategy and Interface Control of Electrocatalytic Carbon Dioxide Reduction Electrodes

Zheng Zhang; Xiaoqiang Guo; Xiaoming Zhang; Shuangjie Liu

doi:10.7536/PC20250708

Progress in Chemistry ›› 2026, Vol. 38 ›› Issue (4) : 741-755 DOI: 10.7536/PC20250708

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Research on the Construction Strategy and Interface Control of Electrocatalytic Carbon Dioxide Reduction Electrodes

Zheng Zhang ¹^,²^,^*
, Xiaoqiang Guo ¹^,²
, Xiaoming Zhang ¹^,²
, Shuangjie Liu ³^,^*

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Abstract

Electrochemical carbon dioxide reduction reactions （CO₂RR） have become an important means of building sustainable energy systems due to their potential to convert carbon dioxide into high-value chemicals under mild conditions， as global carbon dioxide emissions become increasingly serious. This review provides a systematic overview of the research progress in the construction of CO₂RR electrodes， with a focus on the structural design principles of the electrodes. It highlights typical construction strategies for metal-based， carbon-based， and emerging electrode structures， analyzing the effects of conductivity， pore structure， and three-phase interface stability on electron transport， carbon dioxide mass transfer， and product desorption behavior.It particularly emphasizes the crucial role of surface and interface engineering in enhancing catalytic selectivity and long-term stability， and summarizes cutting-edge construction methods such as 3D printing， bio-inspired modification of electrodes， and the use of derivative materials. Although existing research has made significant progress under laboratory conditions， challenges such as structural stability， construction costs， and large-scale manufacturability remain to be addressed in practical applications. Therefore， this review proposes that future research should be conducted in a coordinated manner in the areas of interface microenvironment control， structural modeling， and manufacturing process simplification to achieve efficient， stable， and scalable CO₂RR electrode systems.

Contents

1 Introduction

2 CO₂RR mechanism

3 CO₂RR electrode construction

3.1 Transition metal-based

3.2 Carbon-based

3.3 Emerging structures and 3D printed electrodes

4 Surface and interface engineering

5 Conclusion and outlook

Graphical abstract

Keywords

CO₂ reduction reaction / electrode construction / interface modulation / carbon neutralization

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Zheng Zhang, Xiaoqiang Guo, Xiaoming Zhang, Shuangjie Liu. Research on the Construction Strategy and Interface Control of Electrocatalytic Carbon Dioxide Reduction Electrodes. Progress in Chemistry, 2026, 38(4): 741-755 DOI:10.7536/PC20250708

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1 Introduction

With the continuous growth of global energy demand and the increasingly severe climate issues caused by greenhouse gas emissions, achieving carbon neutrality has become one of the core goals for global sustainable development^[1-2]. Carbon dioxide (CO₂) as one of the most major greenhouse gases, its efficient conversion and utilization not only helps alleviate environmental pressure but also provides a new pathway for the high-value conversion of renewable energy^[3]. The electrocatalytic carbon dioxide reduction reaction (CO₂RR), serving as a bridge connecting renewable electricity and carbon resource cycling, is considered one of the important technologies to mitigate greenhouse gas emissions and fossil energy shortages, and has received widespread attention in recent years. Electrocatalytic CO₂RR offers advantages such as controllable processes, diverse reaction pathways, and environmental friendliness, capable of converting CO₂ into carbon monoxide (CO)^[4-5], methane (CH₄)^[6], formic acid (HCOOH)^[7-9], as well as ethylene (C₂H₄)^[1,10-11], ethanol (C₂H₅OH)^[1]and various other high-value-added chemicals and fuels, holding promise to be combined with mature technologies such as industrial electrolyzers to construct a modular, distributed green chemical industry system.

In electrocatalytic CO₂RR, the electrode serves as a bridge between the external circuit and the reaction medium; its primary role is to provide electrons to drive the reduction reaction, where CO₂molecules receive electrons and combine with protons to generate reduction products^[11-12]. The conductivity of the electrode, its surface electronic structure, and its interfacial properties with the catalyst all significantly affect electron transfer efficiency, thereby altering the reaction rate and pathway. However, CO₂RR catalytic electrodes still face key challenges such as bubble accumulation and poor stability of the three-phase interface, mass transfer limitations and insufficient CO₂supply, competition from side reactions (hydrogen evolution reaction), inadequate stability, and difficulties in regulating surface hydrophilicity/hydrophobicity^[12-16], which severely restricts the improvement of CO₂RR reaction efficiency and the advancement of industrialization. Therefore, the rational design and construction of efficient electrode systems has become an important direction in current CO₂RR research.

In recent years, with the development of materials science and interface engineering, various novel CO₂RR catalytic electrode construction strategies have emerged. For instance, transition metals and their compounds exhibit excellent CO₂RR performance due to their tunable d-orbital electronic structures^[4,17-19]; carbon-based materials have become important catalyst supports owing to their high conductivity, structural diversity, and functionalizability^[20-22]; furthermore, emerging three-dimensional porous electrodes^[13], gas diffusion electrodes (GDE)^[3,23-24]and other such structures have demonstrated great potential in enhancing catalyst loading and improving mass transport. Meanwhile, interface engineering methods such as surface modification, heterostructure construction, and in-situ reduction techniques are continuously being introduced to optimize the synergistic effects between catalysts and electrolytes^[11,25-27], thereby enhancing the activity, selectivity, and stability of the electrocatalytic CO₂RR reaction.

This article will focus on CO₂RR electrode construction to provide a systematic review, first briefly introducing the basic reaction mechanisms and evaluation metrics of CO₂RR, then proceeding from the types of electrode materials to organize research progress in transition metal-based, carbon-based, and novel three-dimensional structure electrodes in recent years, with a key discussion on the mechanism of interface engineering in enhancing electrode performance. Finally, combining current research hotspots and practical application needs, it analyzes the main challenges faced by CO₂RR electrode construction and looks forward to possible future development directions. This review provides theoretical reference and practical guidance for building efficient and stable CO₂RR electrode systems.

2 CO₂RR mechanism

Electrocatalytic CO₂RR occurs at the electrode-electrolyte interface, where an applied potential drives the co-reduction of CO₂molecules involving multiple electrons and protons. Due to the stable linear structure and high activation energy barrier of CO₂molecules, their electron orbitals cannot directly accept electrons; thus, activation relies on active sites provided by the electrode surface, electron enrichment capabilities, and local electric field effects.^[28]. During the reaction process, CO₂first adsorbs onto the catalyst surface. Through electron injection and concerted proton transfer, key reaction intermediates such as carboxyl (*COOH) and hydroxymethyl (*CHO) are formed (Table 1)^[29].

During the electrocatalytic carbon dioxide reduction process, CO₂ molecules can be converted into various carbon-based products along different reaction pathways after activation. The specific product formed depends on the stability of intermediates on the catalyst surface and the selectivity of subsequent electron-proton transfer steps. Depending on the number of electrons and protons transferred during the reaction, common reduction products include CO, HCOOH, methanol (CH₃OH), methane (CH₄), and multi-carbon products (C₂₊) such as C₂H₄ and C₂H₅OH, etc.^[26,30-35](Table 2).

In the aforementioned CO₂RR, the generation of typical products such as CO, HCOOH, CH₄, C₂H₄involves complex coupled electron-proton transfer processes, with specific pathways jointly regulated by the adsorption strength of intermediates on the catalyst surface and reaction energy barriers. Although significant progress has been made in enhancing catalyst activity through extensive research, in practical electrolysis systems, the catalyst must be highly coupled with the electrode structure, and its overall performance is further constrained by multiple factors including electron transport efficiency, gas and electrolyte mass transfer behavior, and interfacial stability.^[29,36]The electrode not only serves as a support carrier for active sites but also directly influences reactant supply and product migration through its structural characteristics, thereby regulating the overall reaction kinetics. Therefore, systematically conducting research on optimizing electrode construction strategies is of great significance for improving the activity, selectivity, and long-term stability of CO₂RR. Based on this, the following section will systematically review and discuss electrode design principles and specific construction methods.

3 CO₂RR electrode construction

3.1 Transition metal-based

3.1.1 Copper-based materials

Copper-based materials exhibit unique C₂ generation capabilities in CO₂₊RR due to their weak adsorption of H and moderate adsorption of CO^{[14,26,37-40]}. However, pure copper substrates typically exhibit low selectivity for C₂₊ products due to size limitations. To enhance the selectivity and activity of copper electrodes in C-C coupling and product distribution, researchers have employed interface modification to overcome size limitations and increase abundant reaction sites^[30,41-42]; utilized morphology control to increase gas contact area, accelerate reactions, and improve reaction efficiency^[5]; and proposed various material design strategies for optimizing the reaction microenvironment^[11,43-45].

Li et al.^[26]modified the surface of copper electrodes by introducing the metal-organic framework (MOF) material UiO-66. During electrolysis, UiO-66 was in situ converted into amorphous ZrO_x, forming an a-ZrO_x/Cu dual-site heterogeneous interface (Fig. 1A~C). This interface effectively stabilized the top-site adsorbed *CO intermediate, increased its surface coverage, and thereby promoted the C-C coupling process. At -1.05 V (vs. RHE), the Faradaic efficiency (FE) for C₂₊products on the modified electrode reached up to 74%, with intrinsic activity nearly doubled compared to bare copper, indicating that the construction of the heterogeneous interface played a crucial role in stabilizing key intermediates and regulating the reaction pathway (Fig. 1D~F). In the GDE system, Daems et al.^[24]achieved controlled soft-landing deposition of CuO_xnanoparticles using sputtered vapor phase polymerization source technology. By adjusting the oxygen flow rate and deposition time, the mass loading and film morphology of the nanoparticles were precisely controlled. The results showed that densely packed CuO_xfilms could enhance the secondary adsorption capacity of *CO, strengthen C-C coupling, and in 1 mol/L KHCO₃, achieved a C₂₊product FE of 76% and an ethylene partial current density of 231 mA/cm²; whereas the rough three-dimensional network structure was more favorable for methane generation, demonstrating the significant regulatory effect of catalytic layer morphology on product selectivity. The organic ligand functionalization strategy also provides an effective pathway for enhancing C₂₊selectivity.

Wang et al.^[46]introduced three amino-functionalized polymers with different pK_avalues (poly-L-lysine, poly-L-histidine, poly-L-arginine) onto copper surfaces via electrodeposition to construct Cu-polymer composite electrodes. Among them, the Cu-PLL composite electrode exhibited optimal performance; its surface uncoordinated amino groups increased the local pH, enhancing *CO intermediate accumulation and C-C coupling, achieving a C₂₊FE of 74.3% at -0.98 V (vs. RHE). Tsai et al.^[47]constructed CuO-MgO nanocomposites, utilizing the in situ dissolution reaction of MgO induced by CO₂and water during the CO₂RR process to obtain a nanoporous copper electrode with high specific surface area. This electrode demonstrated excellent catalytic performance at high current densities, achieving a C₂product FE of 49.6% at an operating voltage of 3.2 V, with ethylene as the main product and the HER side reaction effectively suppressed, indicating that its high specific surface area and three-phase interface accessibility play a significant promoting role in CO₂RR. Furthermore, Lv et al.^[48]synthesized Cu(OH)₂precursors via ammonia solution precipitation, followed by heat treatment and electrochemical reduction to obtain a highly porous copper electrode (Figure 1G). The resulting catalyst had a pore size distribution of 100~200 nm, forming three-dimensional interconnected channels that significantly increased the gas-liquid-solid interfacial reaction area. Meanwhile, the high exposure of its Cu(111) facets favored the stable adsorption of *CO intermediates (Figure 1H~J). At a potential of -0.67 V (vs. RHE), the catalyst achieved a 62% FE for C²products even at a high current density of 653 mA/cm₂₊ (Figure 1K~M). In summary, the unique advantages of copper-based materials in forming multi-carbon products have been fully realized through diverse interface engineering and microstructural optimization.

Future efforts can further advance the construction of heterogeneous interfaces, morphology control, organic ligand modification, and porous architecture design; focus on regulating the adsorption behavior of key intermediates and optimizing C-C coupling pathways; combining advanced characterization techniques with machine learning-assisted design will help reveal reaction mechanisms, screen high-performance Cu-based materials, and facilitate their rational design and scalable preparation.

3.1.2 Zinc, silver, and tin-based materials

In CO₂RR, zinc, silver, and tin-based materials have become important catalytic systems for low-carbon products due to their excellent selectivity for two-electron products such as CO and HCOOH, as well as their lower reaction overpotentials.^[49-50]. Due to their relatively low CO adsorption strength, these metals facilitate the timely desorption of the *CO intermediate, thereby preventing subsequent hydrogenation to form multi-carbon products, making them more suitable for precisely regulating the generation of low-carbon products. Researchers have constructed metal-metal or metal-nonmetal heterostructure interfaces (such as Ag-Cu, Sn-Zn, or Sn-SnO_x, etc.)^[37,51-54], generating electron redistribution and local electric field effects at the interface, which enhance the density of reactive sites and the ability to regulate intermediate adsorption. By doping with transition metals (such as In, Bi, Ni, etc.) or non-metallic elements (such as S, N, P) to modulate the lattice structure and electronic configuration of the materials, the reaction pathways can be effectively adjusted and key intermediates stabilized.^[9,18,55-56].

Lou et al.^[4]By constructing Zn-based electrodes with a highly porous structure, high-selectivity synthesis of CO products was achieved, while demonstrating significant resistance to HER (Figure 2A). This catalyst uses Zn foil as the starting material; it is first pickled with acid to remove the surface passivation layer, and then treated with alkali to induce the formation of abundant micro-nano pore structures on its surface (Figure 2B, C). The resulting porous Zn catalyst possesses a high specific surface area and complex surface topology, significantly enhancing CO₂ molecular adsorption and electrolytic reaction activity. Interface structure analysis reveals that the etching-induced Zn-enriched layer not only stabilizes the formation of COOH* intermediates but also weakens the proton-electron coupled HER pathway (Figure 2D). At a potential of -1.05 V (vs. RHE), this porous structured catalyst achieved a CO Faradaic efficiency of 93% and maintained stable product distribution during long-term operation (Figure 2E). Density functional theory calculations and in situ Raman analysis results further confirm that the local electric field enhancement induced by the porous structure and the regulation of electronic states at reaction sites are key factors for the improved CO selectivity (Figure 2F).

Zhang et al.^[18]reported an AgSn-SnO₂heterogeneous nanosheet electrode that achieved efficient and stable formate selective production in CO₂RR (Figure 2G). The electrode was constructed in situ on a carbon cloth substrate via a one-step hydrothermal method, generating vertically aligned AgSn-SnO₂nanosheet arrays. This hierarchical structure provides excellent gas diffusion channels and electrolyte penetration pathways, forming a stable gas-liquid-solid three-phase interface, which facilitates improved CO₂molecule mass transfer efficiency (Figure 2H). In terms of interface engineering, Ag atoms are doped into the SnO₂lattice to form stable Ag-O-Sn electronic synergistic sites, effectively regulating the catalytic surface electron density distribution, thereby enhancing the adsorption stability of the HCOO* intermediate and steering the reaction pathway towards formate production (Figure 2I~L). At a potential of -1.6 V (vs. RHE), the electrode exhibits an FE as high as 97% for HCOOH production, and maintains significant electrocatalytic stability even at ampere-level current densities (1.0 A/cm²) (Figure 2M, N). Furthermore, through the electroreduction process under weakly acidic conditions, this system can achieve the production of pure formic acid liquid at high concentrations (3.2 wt%), demonstrating promising industrialization potential (Figure 2O, P). Overall, both Ag- and Sn-based catalysts demonstrate highly efficient capabilities in regulating reaction pathways and stabilizing intermediates through interface coupling (such as constructing Ag-O-Sn sites) and surface morphology control (such as inducing micro-nano pores). Such electrodes possess long-term operational stability under high current densities and weakly acidic environments, offering realistic prospects for scaling up from laboratory to industrial applications.

With the development of electrocatalytic CO₂RR technology, electrodes based on transition metals such as Zn, Ag, and Sn are increasingly becoming viable for engineered applications in CO₂conversion processes. Future work can further explore the microscopic mechanisms of dual-/multi-metal synergistic interfaces in regulating reaction energy barriers, and systematically optimize electrode configurations by combining factors such as gas diffusion layers and interfacial hydrophobicity, thereby promoting the practical deployment and scaled production of such electrodes in carbon-neutral energy systems.

3.2 Carbon-based

3.2.1 Carbon Cloth, Carbon Paper, and Carbon Felt

Carbon cloth, carbon paper, and carbon felt, as typical carbon-based support materials, have been widely used in the construction of various electrocatalytic electrode systems due to their excellent electrical conductivity, good mechanical flexibility, and tunable surface chemical properties^[57-58]. These materials not only provide effective electron transport pathways to ensure efficient charge transfer during catalytic reactions but also possess large specific surface areas and porous structures that facilitate reactant diffusion and adsorption, thereby enhancing reaction rates. Furthermore, carbon material surfaces are rich in functionalizable sites; through doping, heat treatment, or surface modification, their electronic structures and surface hydrophilicity/hydrophobicity can be further regulated, providing a highly controllable interface environment for loading diverse catalysts^[59].

Beatriz et al.^[60]By modulating the coordination environment between metal phthalocyanine (MPc, M = Fe, Co, Ni) molecules and carbon cloth, a series of carbon paper-supported metal phthalocyanine electrodes were constructed for efficient catalysis of CO₂RR. This system employs liquid-phase self-assembly to uniformly load MPc onto the carbon paper surface, followed by heat treatment to guide the formation of stable π-π interactions and partial electronic coupling between the M-N₄active centers and the carbon support. Modulation of different metal centers alters the electronic structure and the adsorption behavior of CO₂intermediates, thereby regulating the reaction pathway and final product distribution (Figure 3A). Surface morphology results show that metal phthalocyanines present a uniformly dispersed sheet-like structure on the carbon paper surface, avoiding aggregation and active site shielding issues, thus ensuring interfacial accessibility for the reaction (Figures 3B~E). The CoPc@carbon paper system exhibits a CO FE as high as 84% at -1.3 V (vs. RHE), outperforming FePc and NiPc configurations, and maintains stable output of current density and selectivity during prolonged electrolysis (Figures 3F, G). Its superior performance is attributed to the moderate adsorption energy of the Co center for the COOH* intermediate and a lower generation energy barrier. Furthermore, this self-supporting structure avoids electron transport hindrance and active site coverage caused by traditional binders (such as Nafion), thereby achieving higher utilization of catalytic sites. This study not only demonstrates the feasibility of carbon paper as a high-performance electrode support but also highlights the critical role of electronic coupling between molecular catalysts and carbon supports in regulating reaction pathways.

Classic carbon-based supports such as carbon cloth, carbon paper, and carbon felt have been widely applied in the battery and energy fields. With the continuous evolution of electrocatalytic CO₂RR technology towards high efficiency, low cost, and scalable applications, carbon-based support materials will also become an important choice. Future research will not only focus on enhancing their intrinsic conductivity and mechanical strength but will also emphasize precise regulation of their multi-scale structures and surface functionalization, such as constructing three-dimensional hierarchical porous networks, introducing macroscopic directional alignment or micro-nano scale surface rough structures, creating defect sites, or incorporating heterostructures like graphene and carbon nanotubes (CNTs). This aims to further enhance the synergistic effects of gas diffusion, product desorption, and interfacial reactions, thereby improving the CO₂RR efficiency and stability of carbon-based electrodes under high current density conditions.

3.2.2 Graphene and Carbon Nanotube Films

Graphene and CNT composite films, as a new generation of high-dimensional carbon-based materials, leverage their excellent electronic conductivity, superior structural flexibility, and high specific surface area in CO₂RR flexible electrode development, demonstrating significant application potential^[61-64]. Particularly in constructing layered heterostructures, introducing transition metal active components, and regulating C-C interfacial coupling behavior, researchers have achieved significant progress in the synergistic optimization of catalytic selectivity and production efficiency^[20,22,65]. Compared with traditional carbon cloth and carbon paper materials, these high-dimensional composite carbon materials provide greater design freedom at the atomic scale, more fully expose catalytic sites, and offer a new platform for the precise regulation of efficient catalytic systems^[66].

Zhou et al.^[20]successfully prepared flexible thin-film electrodes consisting of CNTs modified with a reduced graphene oxide layer (RGOL) and polyphenylene sulfide (PPS) doped with reduced graphene oxide (RGO) using solution mixing and hot-press film formation techniques, and further constructed Cu₂O nanocrystal catalytic layers on their surface via electrodeposition (Figure 4A). The results show that the synergistic effect between CNTs and graphene enhanced the conductivity and mechanical toughness of the PPS substrate, while the introduction of Cu₂O provided the metal oxide active sites required for CO₂RR. The electrodeposited Cu₂O exhibited a facet-exposed structure with particle sizes of approximately 50–150 nm (Figure 4B–E), ensuring effective contact between electrons and reactants at the interface, holding promise for efficient conversion of C₁products such as CO or HCOOH (Figure 4F). Zhang et al.^[22]introduced Co-MnO heterogeneous nanoparticles as electrocatalytic centers synergistically into a three-dimensional conductive scaffold supported by a graphene/CNT hybrid network, preparing a highly active flexible bifunctional electrode material (Figure 4G). This composite structure in situ loaded metal oxides onto the graphene/CNT surface via a one-step hydrothermal synthesis method, forming a porous interconnected network that effectively improved catalyst dispersion and electron conduction pathways (Figure 4H). Although this electrode was applied to the oxygen evolution reaction in zinc-air batteries, its interfacial synergistic effects and construction strategy with carbon materials are equally applicable to stabilizing reaction intermediates and controlling gas product desorption in CO₂RR systems. It exhibited high current density and low overpotential in 0.1 M KOH, reflecting its excellent electronic regulation and interfacial transport capabilities. Meanwhile, Geng et al.^[65]introduced acid-treated multi-walled CNTs and NiCo₂S₄nanoparticles together into graphene interlayers through solution filtration and hydrothermal treatment processes, constructing a three-dimensional conductive scaffold structure (Figure 4I). Among them, NiCo₂S₄particles were uniformly attached to the surface of graphene sheets, while CNTs served as support and connection units, effectively inhibiting graphene sheet aggregation and enhancing interfacial openness (Figure 4J, K). This flexible thin film demonstrated excellent electrochemical performance, achieving a specific capacitance of 2.34 F/cm²at 0.2 mA/cm²) (Figure 4L), demonstrating exceptional charge storage and transport capabilities, providing a structural foundation for building deformable electrocatalytic devices.

Graphene and CNTs demonstrate synergistic enhancement potential in the construction of electrocatalytic electrodes, providing broad opportunities for developing high-performance, tunable catalytic interfaces. Future efforts urgently need to focus on developing low-cost, green, and controllable preparation technologies to achieve macroscopic uniformity and interface quality control of their composite structures. Furthermore, synergistic construction of multifunctional composite systems with other functional materials (such as MOFs, COFs, conductive polymers, etc.) should be pursued to realize structure-performance coordinated regulation, thereby further improving product selectivity and device practicality.

3.2.3 Carbon Aerogels and Carbon Foams

Carbon aerogels and carbon foam materials, as novel three-dimensional carbon supports, possess highly open porous network structures, continuous interconnected conductive pathways, and excellent structural tunability^[67-69]. Unlike conventional two-dimensional carbon-based materials, carbon aerogels can be prepared from organic precursors such as natural polysaccharides, phenolic resins, and polyacrylonitrile via a sol-gel process to yield lightweight, high-porosity, and mechanically flexible scaffold structures. The synergistic effect of their micropores and mesopores facilitates the construction of stable gas-liquid-solid three-phase reaction interfaces, significantly enhancing CO₂molecule capture efficiency and the stability of reaction intermediates^[23]. Meanwhile, carbon foams feature larger pore sizes and higher volumetric conductivity, making them particularly suitable for practical device conditions that require loading high-density catalysts while maintaining good reaction flux.

Zhang et al.^[23]developed a biomass carbon aerogel electrode based on cellulose aerogel for highly selective CO₂RR. This system uses natural cellulose as a precursor to obtain a three-dimensional network aerogel skeleton through freeze-drying, followed by a ZnCl₂-assisted pyrolysis strategy to complete the carbonization process (Figure 5A). The introduction of ZnCl₂not only induced the formation of abundant microporous structures during the carbonization process but also regulated the defect density and active site types on the surface of the carbon aerogel (Figure 5B). The resulting carbon aerogel possesses a highly open pore structure and a hierarchical cross-linked network, demonstrating good electrolyte permeability and CO₂molecule accessibility in electrode construction (Figure 5C). Long-term electrolysis experiments showed that this carbon-based electrode exhibits excellent structural durability and electrochemical stability. In terms of interface morphology, the ZnCl₂-assisted carbonization process significantly increased the pore volume and specific surface area of the carbon material, enabling uniform distribution of metal single atoms within the skeleton and forming stable M-C or M-N bonding interfaces, which enhanced charge transfer efficiency and catalytic reaction site activity (Figures 5D~F).

The future development of carbon aerogels will focus on the ordered construction of multi-scale pore structures and the precise regulation of surface functions. Synergy between micrometer-scale frameworks and nanometer-scale channels can be achieved through template methods, self-assembly strategies, or 3D printing technologies, which is expected to further improve gas diffusion and mass transfer efficiency for liquid-phase reactants. Meanwhile, doping with other atoms (such as N, S, P), introducing interfacial defects, or constructing multiphase composite structures via covalent/non-covalent bonding will provide greater scope for regulating their electronic properties and catalytic interfacial reaction environments.

3.3 Emerging Structures and 3D Printed Electrodes

Due to its customizable, multi-scale, and rapid prototyping characteristics, 3D printing technology is widely applied in the field of energy device manufacturing^[70-72], and is gradually becoming an important strategy for constructing novel CO₂RR electrode structures. Unlike traditional electrodes that rely on slurry coating, pressing, and bonding, 3D printing enables precise design of electrode geometry, pore distribution, and material composition at the micro-to-millimeter scale through digitally controlled layer-by-layer deposition, thereby endowing electrodes with enhanced structural permeability and functional integration. In CO₂RR, this method can simultaneously optimize the transport pathways of CO₂gas, electrolyte wettability, charge conductivity, and the distribution state of reactants/products, effectively avoiding interfacial failure issues such as catalytic layer "flooding" and bubble accumulation^[73]. Furthermore, 3D printing exhibits excellent adaptability to non-planar and flexible substrates, making it suitable not only for high-density electrode stacking but also for developing flexible or modular CO₂conversion systems. More importantly, its compatibility with various materials (such as conductive carbon, metal oxides, polymers, etc.) supports the co-printing of composite structures, significantly expanding the dimensions for regulating electrode structural functions^[74-75].

Zhao et al.^[21]developed a 3D printing-based phosphorus-nitrogen co-doped metal-free carbon catalytic electrode (3Dp-PNCE) for CO₂RR to efficiently generate syngas (Fig. 6A, B). This method adheres to green chemistry principles, significantly reducing energy consumption and material waste during manufacturing, demonstrating excellent environmental friendliness and resource utilization efficiency.

Through 3D printing technology, precise configuration control of the electrode structure is achieved, enabling optimal matching in mass transport, electron transfer, and reaction interfaces, thereby significantly enhancing CO₂RR overall efficiency. Performance test results indicate that the electrode achieves tunable H₂/CO ratios (0.58~3.65) within a potential range of -0.6 to -1.0 V, fully meeting the diverse requirements for syngas composition in subsequent Fischer-Tropsch synthesis (Figure 6C). Furthermore, the electrode maintains 94.5% of its initial CO Faradaic efficiency after 10 hours of continuous operation, demonstrating excellent stability (Figure 6D). Compared with traditional fabrication processes, 3Dp-PNCE exhibits lower manufacturing waste emissions and higher design flexibility, fully embodying the potential of 3D printing in green and sustainable electrode manufacturing, providing a new paradigm for the design of customized, high-performance CO₂RR catalytic electrodes. The research team led by Joshua^[13]addressing the demand for efficient generation of C₂₊products in CO₂RR, developed a 3D-printable fluorinated polymer gas diffusion layer (GDL) with tunable microporous structures (Figure 6E). This GDL design aims to enhance the electrode structure's ability to regulate gas transport and product distribution, making it particularly suitable for high current density operating conditions exceeding 300 mA/cm². By systematically regulating the GDL's permeability, microscopic pore structure, macroscopic geometric morphology, and surface roughness (Figure 6F), the pyramid-shaped macroscopic structure can increase the partial current density of C₂H₄by 1.8 times, while the surface morphology design can increase the ratio of C₂H₄to CO products by up to 100 times, significantly enhancing the selectivity for multi-carbon products (Figure 6G). The GDL not only serves as a gas management channel but also significantly influences the behavior of the electrode-gas-electrolyte three-phase interface through structural fine-tuning, thereby achieving precise control over catalytic pathways and product distribution.

3D printing technology in CO₂RR electrode construction shows broad prospects, and its future research can focus on material innovation, intelligent structural design, functional integration, and manufacturing process optimization. By developing high-performance composite inks, constructing multi-scale biomimetic structures, implementing multi-functional integrated printing strategies, and synergistically enhancing high-precision and large-scale fabrication capabilities, it will promote the customized and efficient development of CO₂RR electrode rapid design and industrial implementation, providing strong support for the development of carbon resource electrocatalysis technology.

4 Surface and Interface Engineering

Research on surface and interface engineering in electrode material design continues to deepen, gradually becoming a key means to enhance electrocatalytic and photoelectrocatalytic performance^[76]. By introducing functional layers on the electrode surface and regulating wettability, charge distribution, local electric fields, and reaction intermediate adsorption behavior, researchers have achieved a leap from traditional inert supports to functionalized and intelligent interfaces^[70,77-80]. Especially in terms of microenvironment regulation at the electrode/electrolyte interface, design strategies such as cationic self-assembled layers, charge regulation layers, and hydrophobic water-blocking layers have been widely applied in CO₂RR, nitrogen reduction reactions, oxygen reduction reactions, and other systems, significantly improving product selectivity and energy utilization efficiency^[81-82]. Meanwhile, the rise of artificial enzyme-modified electrodes has provided more bio-inspired strategies for surface engineering. By introducing enzyme-mimicking structures, active centers, or amino acid sites on the electrode surface, artificial enzyme-modified electrodes can not only mimic the high-selectivity substrate conversion behavior of natural enzymes under physiological conditions but also possess excellent electrochemical coupling capabilities and structural stability^[83]. For example, enzyme-mimicking materials such as MOFs, metal clusters, or coordination polymers have also been used to construct electrode functional layers^[84-87], demonstrating advantages in tunable structure and electronic environment, strong interfacial coupling, and multi-functional integration.

Vichou et al.^[12]proposed a strategy for constructing smart electrode surfaces based on the immobilization of imidazolium cation electrolytes, using electrochemical-chemical (IM⁺-EC) and electrochemical-electrochemical (IM⁺-EE) methods to covalently bond [EMIM]⁺and other cations onto carbon-based electrode surfaces, thereby regulating the local electric field strength at the electrode/electrolyte interface (Fig. 7A, B). The immobilized positively charged surface layer not only significantly altered the interfacial microenvironment: the contact angle dropped sharply from 86° to less than 5°, forming a highly hydrophilic interface layer capable of trapping water molecules. ATR-FTIR confirmed its stable hydrated structure, thus optimizing proton supply and CO₂activation conditions. Furthermore, this molecular layer caused almost no hindrance to outer-sphere electron transfer processes but exerted a selective regulatory effect on inner-sphere coordination-dependent reactions, effectively suppressing HER. Through local electric fields and π⁺-π interactions, it achieved "in situ enrichment" of homogeneous Rh complexes, thereby enhancing the conversion pathway from CO₂to formate. Electrochemical tests showed that this strategy not only effectively increased the production rate and selectivity of formate but also significantly reduced HER current density and overpotential, achieving kinetic directional bias. At an industrial-level current density of 100 mA/cm², the formate production rate of the modified electrode reached 4.6 g/(m²·min), and it maintained structural stability after accumulating 9000 C of charge, demonstrating excellent long-term durability (Fig. 7C, D). This work breaks through the solubility and environmental risk issues associated with traditional solution-added ionic liquids, realizing a paradigm shift of ionic liquids from "electrolyte engineering" to "electrode interface engineering."

On the other hand, Chen et al.^[9]constructed a composite photoelectrode based on MOF-derived porous carbon nanorods encapsulating Bi nanoparticles (Bi@C), enhancing the performance of p-type Si nanowire array photocathodes in CO₂photoelectrocatalytic reduction. The porous carbon material not only provides abundant pore structures and high specific surface area to enhance CO₂enrichment at the interface, but also its strongly hydrophobic interface effectively isolates direct contact between the electrode and the aqueous phase, thereby suppressing HER and improving CO₂mass transfer rates (Figure 7E). Meanwhile, as key active sites, Bi nanoparticles can stably adsorb the *OCHO intermediate and promote the selective conversion of CO₂to formate (Figure 7F~H). The Bi@C coating structure not only effectively reduces charge transfer resistance but also eliminates trap states on the Si surface, significantly improving the separation efficiency and interfacial transfer rate of photogenerated carriers; meanwhile, the plasmonic effect of Bi nanoparticles enhances visible light absorption, and XPS results show increased electron cloud density, which favors the formation and stabilization of OCHO. In situ infrared spectroscopy directly captured the characteristic peaks of CO₂^•-and *OCHO, confirming the existence of the formate generation pathway. Under conditions of -0.9 V vs. RHE, the optimal Si-Bi@C800 electrode achieved a formate FE of 91.23% and a yield of 88.5 μmol/(h·cm²) (Figure 7I). These works collectively reveal the importance of precisely regulating the interfacial reaction microenvironment from the perspective of material design.

Surface and interface engineering is one of the most widely applied approaches in the field of catalytic electrode optimization. In the future, surface engineering will transcend traditional roughness regulation and alloying strategies, shifting towards atomic-precision configuration design, including single-atom doping, coordination environment modulation, and surface stress/strain guidance, to optimize the binding strength between reaction intermediates and catalytic electrode surfaces, thereby enhancing CO₂reduction selectivity and activity. Its development will highly depend on the interdisciplinary integration of materials science, computational simulation, artificial intelligence, and engineering technology, while also providing a broader vision for the development of industrial-scale catalytic systems.

5 Conclusion and Outlook

This article systematically reviews the design principles and construction strategies for electrocatalytic CO₂RR electrodes, outlining research progress in enhancing CO₂RR performance through transition metal (copper, silver, tin, indium) materials, carbon-based electrodes (carbon cloth, graphene, carbon aerogels, etc.), emerging 3D-printed structures, and surface/interface engineering. Electrode design has a decisive impact on the reaction efficiency, selectivity, and stability of CO₂RR. The research main thread for CO₂RR electrode engineering spans from intrinsic material properties to hierarchical structural regulation, and further to the synergistic optimization of gas-liquid-solid three-phase interfaces (Table 3).

(1) Material design level

In terms of material selection, different metals and their oxides or alloy systems exhibit specific preferences for reduction products: copper-based electrodes effectively promote C—C coupling to generate multi-carbon products, while silver, tin, and indium are respectively suitable for producing small-molecule products such as CO or HCOOH. By regulating the exposed crystal facets, oxidation states, or constructing nano-scale surface structures of metals, reaction pathways and intermediate stability can be guided at the molecular level, thereby enhancing the selectivity of target products. Secondly, due to advantages such as excellent conductivity, structural flexibility, and low cost, carbon-based electrodes have become important supports for constructing high-performance CO₂RR electrodes. Rational selection of the type and structural form of carbon materials, such as two-dimensional graphene, three-dimensional carbon aerogels, or carbon foams, can effectively regulate the interfacial properties of the reaction environment and the migration paths of reactants/products, further improving catalytic performance.

(2) Structural regulation level

Emerging manufacturing technologies such as 3D printing provide new pathways for the precise construction of electrode macro-micro-nano structures. Digital design enables the acquisition of porous skeletons and uniform current distribution, thereby significantly optimizing mass transfer and product desorption. Surface and interface engineering has also become a crucial link in enhancing performance: hydrophobic modification, fluorination treatment, or constructing CO-affinity₂surfaces can stabilize the gas-liquid-solid three-phase interface, effectively inhibiting product bubble retention and catalyst deactivation; strategies such as heterostructure construction and catalyst coating can enhance electron transport and interfacial synergistic effects, further improving the activity and durability of the electrode.

(3) System Integration Level

Although numerous high-performance electrode systems have achieved excellent activity and selectivity under laboratory conditions, their application in long-cycle, high-current-density, and complex electrolytic environments still faces the following challenges.

① Some construction methods involve complex operations and high costs, limiting the feasibility of electrodes in large-scale manufacturing; ② Interface issues such as catalytic site shielding and bubble blockage caused by gas product accumulation still lack systematic solution strategies; ③ Electrodes may undergo structural reconstruction, catalyst migration, and interface instability during the reaction process, affecting their long-term stability; ④ The multi-scale structure's effect on CO₂The mechanism of mass transfer and intermediate state stabilization still requires in-depth quantitative analysis.

To this end, future research should focus on the following directions to promote CO₂RR electrode systems toward practical application (Figure 8): (1) Develop wide-pH adaptable electrode systems: Design universal electrode materials compatible with acidic, neutral, and alkaline electrolytes to meet the reaction requirements of different coupling systems (such as anodic biomass oxidation or OER); (2) Expand digital manufacturing and structural simulation technologies: Utilize methods such as 3D printing, topology optimization, and multi-physics simulation to achieve precise construction and performance prediction of electrode macro-micro-nano structures; (3) Strengthen in-situ characterization and modeling of three-phase interfaces and bubble dynamics: Employ techniques like electrochemical in-situ imaging and X-ray imaging to deeply analyze the impact of bubble generation, retention, and desorption behaviors on interfacial reaction efficiency; (4) Promote low-cost, high-throughput electrode fabrication strategies: Implement large-area, reproducible high-performance electrode preparation processes using methods such as spray coating, self-assembly, and template-assisted sintering.

In summary, CO₂RR electrode research has advanced from the material optimization stage to a new phase of synergistic design involving multidimensional structures and reaction behaviors. In the future, through the organic integration of structural construction, interface regulation, and engineering integration, efficient, stable, and scalable electrochemical CO₂conversion systems will be provided with a solid foundation, offering key support for sustainable energy systems under the "carbon neutrality" goal.

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