Innovative electrode designs for low-temperature electrochemical CO₂ reduction with ampere-level performance

Xiaofeng Ke ^a, Weicong Xu^a, Chao Liu^a, Yakun Wang^a, Xiaozhong Huang^a, Rui Xiao *^a, Xiaomin Xu *^b, Tao Li *^a and Zongping Shao *^b
aSchool of Energy and Environment, Southeast University, Nanjing, 210000, China. E-mail: 101012902@seu.edu.cn; ruixiao@seu.edu.cn
^bCurtin Centre for Advanced Energy Materials and Technologies (CAEMT), WA School of Mines: Minerals, Energy and Chemical Engineering (WASM-MECE), Curtin University, Perth, Western Australia 6102, Australia. E-mail: xiaomin.xu@curtin.edu.au; zongping.shao@curtin.edu.au

First published on 14th July 2025

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Xiaofeng Ke

Xiaofeng Ke is a PhD candidate at the School of Energy and Environment at South Southeast University, under the supervision of Prof. Tao Li. Her current research focuses on the rational design of novel electrodes for electrochemical CO2 reduction.

Rui Xiao

Rui Xiao is the Dean of the School of Energy and Environment at Southeast University, China. He is also the Changjiang Scholar Chair Professor and the recipient of the National Science Fund for Distinguished Young Scholars. He obtained his PhD from Southeast University in 2005. His research interests focus on energy conversion materials, energy saving, pollutant emission reduction, CO2 capture, utilization, and storage.

Xiaomin Xu

Xiaomin Xu is currently a Senior Lecturer at the Curtin Centre for Advanced Energy Materials and Technologies (CAEMT), WA School of Mines: Minerals, Energy and Chemical Engineering (WASM-MECE), Curtin University, Australia. He received his PhD in Chemical Engineering from WASM-MECE, Curtin University in 2021. His research interests focus on the development of functional materials for application in electrochemical energy storage and conversion, including CO2 conversion, water electrolysis, and metal–air batteries.

Tao Li

Tao Li is currently a professor at the School of Energy and Environment at South Southeast University, China. He received his PhD in Chemical Engineering from Imperial College London, UK, in 2015. His current research interests focus on inorganic ceramic and polymer membrane technology, developing original membrane structure designs and new fabrication processes for new energy technology, green chemical industry, energy saving, and emission reduction applications (fuel cells, carbon capture, utilization, and storage).

Zongping Shao

Zongping Shao is John Curtin Distinguished Professor at WA School of Mines: Minerals, Energy and Chemical Engineering (WASM-MECE) and the Founding Director at the Curtin Centre for Advanced Energy Materials and Technologies (CAEMT), Curtin University, Australia. He obtained his PhD from Dalian Institute of Chemical Physics, China, in 2000. He worked as a visiting scholar at Institut de Researches Sur La Catalyse, CNRS, France, and then a postdoctoral fellow at California Institute of Technology, USA, from 2000 to 2005. His research interests include mixed conducting membranes, solid oxide electrochemical cells, electrocatalysis, solar cells, and advanced energy storage technologies including lithium/sodium-(ion) batteries, metal–air batteries, and supercapacitors. He has been recognized as a Highly Cited Researcher by Clarivate Analytics since 2017.

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Broader context Excessive CO2 emissions have raised growing concerns associated with issues such as global warming, ocean acidification, and biodiversity loss. Transitioning to sustainable energy systems is essential to mitigate these impacts and achieve carbon neutrality. The electrochemical CO2 reduction reaction (eCO2RR) offers a dual solution by converting CO2 into value-added chemicals and fuels while simultaneously supporting renewable energy storage. However, despite its impressive lab-scale success under low-current–density conditions, scaling this technology to industrial-level, high-current–density operations remains a formidable challenge. In this context, advanced electrode design has emerged as a critical strategy to overcome these barriers. Recent developments in novel electrode configurations and upgrading strategies have driven significant progress. This review provides a timely and comprehensive summary of recent methods, breakthroughs, and understandings about functional electrode architectures and reaction interface engineering, aiming to offer actionable guidelines for constructing scalable electrode structures. We focus on optimizing electrode gas–liquid equilibrium modulation under high current densities to enhance mass/electron/proton transport efficiency and reaction kinetics. Beyond summarizing the current progress, we highlight emerging trends, address critical challenges, and offer forward-looking perspectives for industrialization. By bridging fundamental science with practical engineering principles, this review aims to accelerate eCO2RR technological translation from laboratory prototypes to real-world applications, ultimately contributing to a carbon-neutral energy future.

1. Introduction

The energy demands of the growing population and frequent social activities heavily rely on fossil fuels, which leads to significant carbon dioxide (CO₂) emissions and, consequently, climate change. Therefore, sustainable development strategies must be considered to reduce greenhouse gas emissions and adopt eco-friendly lifestyles.^1–3 The development of emerging technologies for carbon capture, utilization, and storage (CCUS) is in high demand, driven by the ‘net zero’ concept proposed by the 2023 United Nations Climate Change Conference (COP28). Thus, the electrochemical CO₂ reduction reaction (eCO₂RR) has become an attractive method for CO₂ utilization, which is capable of converting CO₂ into dispatchable fuels and value-added chemicals and is an effective route for achieving a low-carbon cycle, which also makes this technology profitable (Fig. 1).^4,5 According to the temperature dependence of the eCO₂RR, electrolyzers are generally divided into two categories: high-temperature (600–800 °C) solid oxide electrolyzers^6,7 and low-temperature (25–80 °C) electrolyzers.⁸ Substantial progress has been made in the electrolysis of CO₂ to carbon monoxide (CO) at high temperatures using ion–conductive solid oxide electrolytes, which is described in detail elsewhere.^6,9–11 The low-temperature eCO₂RR is considered an environmentally friendly process, which converts CO₂ into value-added chemicals and fuels (e.g., CO, formic acid, methane, methanol, ethylene, and ethanol) through an electrocatalytic process at ambient temperature and pressure. Over the past decades, research on the eCO₂RR has seen tremendous development with a narrow focus on the electrocatalyst itself and in terms of a more comprehensive combination of reactor design and systems engineering, which has accelerated the rapid development of low-temperature electrolyzers for practical application.^12–16

In the eCO₂RR process, CO₂ is transported as a gaseous feedstock to an electrochemical reactor (also known as an “electrolyzer” or “cell”), where it undergoes a reduction reaction on the surface of a catalyst under the influence of an applied potential. Compared with other relevant technologies for reducing excess CO₂ emissions, eCO₂RR offers several advantages, including cleanliness, environmental friendliness, precise reaction control, simple device setup, and mild operating conditions.^17,18 Conversely, the scientific field of CO₂ electrocatalysis still faces numerous critical challenges including reducing the cell voltage, ensuring stability, and achieving industrial-scale current densities with high energy and carbon efficiencies. Advanced electrocatalyst designs and optimization of CO₂ electrolyzer systems are essential for overcoming the challenges faced in industrial applications. To date, numerous studies have focused on eCO₂RR catalyst designs, which have been summarized in several comprehensive reviews.^19–23 However, the structure of the electrodes has often been overlooked despite its crucial role in practical applications, which require high current density, proper conversion rate, adequate productivity, and stable operation. Therefore, the design of effective electrodes and reactors is significant.^24–26

With the rapid development of low-temperature eCO₂RR technology, the design of electrodes has received extensive attention and continuously explored. The electrode assembly is a key feature of electrochemical CO₂ conversion systems, affecting the mass transfer process of CO₂ or protons. During the past few decades, conventional two-dimensional (2D) working electrodes in H-cells, namely non-gas diffusion electrodes (GDEs), have been almost exclusively adopted, which need to be immersed into the electrolyte solution; and CO₂ gas is transported to the surface of the electrode for the reduction reaction by dissolving in the electrolyte.^27,28 However, although some catalysts have demonstrated impressive activity, the reaction rates are limited by the low solubility of CO₂ in aqueous solution (34 mM at 25 °C and 1 atm), the slow diffusion of CO₂ in aqueous systems, and the thick mass transfer boundary layer, which hinder gas transport.^24,29–32 Therefore, the current density of the reaction is usually limited to 100 mA cm⁻², which is far below the industrial-scale current density (200 mA cm⁻²).^33–35 In addition, the traditional electrode structure is prone to blockage from impurities after long-term operation, thus hindering CO₂ from reaching the catalytic active sites, affecting the kinetics of eCO₂RR and stimulating the hydrogen evolution reaction (HER).^36–38 Therefore, alternative electrode assemblies are necessary to fulfill the industrial requirements and achieve practical applications.

GDEs were first proposed in fuel cells and later introduced in CO₂ electrocatalysis applications, which transport CO₂ through a porous medium, effectively shortening the gas diffusion path and increasing the gas concentration near the electrocatalyst.^39,40 High current densities in low-temperature CO₂ electrolyzer systems are in demand. In flow cell systems, CO₂ can be rapidly transported through the gas diffusion layer on the catalyst surface and the active site can receive the proton and electron transfer required. Planar GDEs can overcome the mass transfer limitations and enhance the triple-phase interface reaction in this system, thus improving the performance of eCO₂RR.^41,42 The adoption of planar GDEs has provided new conceptual design and operating principles for reactors in eCO₂RR technology. The performance of these vapor-fed reactors is approaching that expected for commercial technology, as described in numerous contemporary studies.^8,43–46 Compared to conventional non-GDEs, planar GDEs have made significant improvement, where recent studies have recorded partial current densities surpassing 1 A cm⁻² for ethylene and CO production.^41,45,47 However, planar GDEs still have some inherent limitations that prevent them from large-scale eCO₂RR applications.⁴⁸ For example, sufficient surface hydrophobicity must be maintained in the system to prevent frequent flooding.⁴⁹ Alternatively, there are issues associated with (bi)carbonate precipitation formed through the interaction between CO₂ and the electrolyte solution, which leads to pore blockage and inactivation of GDEs.^45,50 Additionally, the preparation process of planar GDEs is relatively complicated, with the effective area of GDEs limited by the size of the reactor.⁵¹ Therefore, novel electrode configurations featuring simplicity, higher active surface area, and modified stability can improve the overall performance of the reaction system.

Three-dimensional (3D) tubular GDEs have received great research attention due to their unique benefits including increased specific surface area and number of catalytic active sites, as well as a tunable pore structure to provide a convenient mass transfer channel.⁵² Furthermore, the fabrication of microtubular GDEs with a diameter in the range of 0.5 mm to 3 mm is a mature process. Tubular electrodes can be used in the study of eCO₂RR and have achieved remarkable progress. Thus far, the record partial current density for ethylene production surpasses 2 A cm⁻², and the utilization of microtubular GDEs can significantly increase its production via eCO₂RR.⁵³ Many reports have also indicated that microtubular GDEs can relatively easily achieve ampere-level eCO₂RR.^52–54 Accordingly, the further exploration and optimization of the structure of microtubular GDEs will endow them with potential to achieve the electrocatalytic conversion of CO₂.

Currently, with the booming development of the eCO₂RR, many reviews^55–61 are available on useful reactor design guidelines.⁶² However, these reviews mainly discussed electrode-component electrocatalyst design^20,23,63 or focused on the structural type of a single electrode.^39,50,64 Therefore, this review will provide a more comprehensive overview of the current status of the electrode structure and CO₂ reactor design, analyzing from conventional non-GDEs and planar GDEs to microtubular GDEs, especially considering their market scale and economic feasibility.

In this review, we present a comprehensive overview of the design principles and structural optimizations for electrode configurations used in low-temperature CO₂ electrolyzers, together with strategies for scaling up these systems for value-added chemical production and insights into commercial development trends. Initially, we outline the cell configurations and underlying fundamental principles for the design of electrode assemblies, ranging from conventional non-GDEs to planar GDEs and microtubular GDEs, discussing key elements such as cell components, performance metrics, reaction mechanisms, and cathode eCO₂RR kinetics. Next, we provide an in-depth analysis of the structural designs and fabrication methods for these electrode types, emphasizing their mass transfer mechanisms and overall impact on electrolyzer performance. Furthermore, we review the latest research progress and application potential of various electrode architectures for generating value-added products, particularly focusing on the advancements in planar GDEs and microtubular GDEs. Finally, we address the challenges confronting the industrialization of eCO₂RR technology and explore future research directions, offering a forward-looking perspective that identifies the advancements needed to ensure both the technical and economic viability of CO₂ utilization via the eCO₂RR process.

2. Operating principles and reactor designs for cathode electrodes in eCO₂RR

The electrocatalytic CO₂ reduction reaction provides a pathway to produce high-value chemicals and fuels with only water and renewable electricity as inputs and has been widely recognized as a promising way to achieve sustainable CO₂ utilization.^65,66 The eCO₂RR process involving critical performance metrics, such as partial current density, product selectivity, lifetime, energy efficiency (EE), and CO₂ conversion, is highly dependent on the efficiency at which its reaction steps are carried out.^67,68 Therefore, understanding these mechanistic steps is fundamental and critical for developing more advanced electrodes. Meanwhile, the designed electrodes need to be coordinated with the configuration of the electrolyzer to ensure that the reaction efficiency is maximized and commercially viable applications will be achieved. In this section, we review the typical theoretical process of eCO₂RR at the electrode, the electrolyzer configuration, and the key performance metrics.

2.1 Electrolyzer configurations

The CO₂ electrolyzer is the site for the electrolytic reaction of CO₂ to produce chemicals (e.g., ethylene or ethanol), which requires multiple reaction steps with incumbent processes. Thus, the optimization of this reaction unit can significantly improve the overall catalytic performance. The development of eCO₂RR reactors has undergone iterative upgrades, as well as the refinement of research objectives and the pursuit of higher performance metrics. CO₂ electrolyzers are usually divided into three configurations, as follows: (i) H-cells,^69,70 (ii) flow cells with a flowing electrolyte and GDE,^71,72 and (iii) membrane electrode assemblies (MEAs) with a solid-state electrolyte or electrolyte free,^73,74 the details of which are summarized as follows.

2.2 Key performance metrics

Regardless of its configuration, a viable eCO₂RR electrolyzer should satisfy several important performance metrics, which are usually used to assess system activity, selectivity, stability, and CO₂ single-pass conversion. They are influenced by factors such as electrode design, catalyst characteristics, electrolyte media, and reactor type. This section will provide a brief overview of some essential key performance metrics.

2.3 Fundamental reaction mechanisms on the electrode for eCO₂RR

The eCO₂RR typically occurs at a three-phase interface (electrode/electrolyte/gas) and has a complex reaction mechanism involving multiple couples of proton (H)–electron transfer, different surface adsorption modes, and numerous possible intermediates/products (Fig. 4).^98–100 In the eCO₂RR process, different hydrocarbons and oxygenate products can be produced by transferring different numbers of electrons (e.g., 2, 4, 6, 8, 12, 14 electrons).¹⁰¹ Table 1 lists the reaction equations for the CO₂ reduction to various products and corresponding equilibrium potentials. It is worth noting that the actual potential required to drive the reduction reaction is usually higher than the aforementioned equilibrium potential. Thermodynamically, producing a specific target product with proper selectivity remains challenging due to the small potential difference between the various reaction routes, resulting in the possibility of different by-products being formed.

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Generally, eCO₂RR undergoes four major steps at the electrode, as follows: (1) diffusion of CO₂ molecules to the electrode surface and their adsorption and activation on the active site, (2) the activated CO₂ molecules form *OCHO/*COOH intermediates via proton–electron transfer (where * denotes a surface active site), (3) conversion from *OCHO/*COOH into final products or *CO intermediate, which then undergo C–C coupling to form different C₂₊ products, followed by possible rearrangement of the product configuration, and (4) desorption and diffusion of the final product from the catalytic active site into the electrolyte solution.^38,102

3 Design of electrode assemblies

The electrode, serving as the core component of an electrolyzer, is the critical reaction site in any eCO₂RR system. From the viewpoint of the electrode functional structure, the electrodes consist of a catalyst layer and a conducting substrate. Several strategies have been investigated for electrocatalysts to determine their effect on the eCO₂RR reactivity and product selectivity. However, once the reaction activity of the catalyst has been increased, the relatively low CO₂ concentration at the electrode surface becomes the key limiting factor in the eCO₂RR rate. As a good electronic conductor and gas diffuser, the electrode is loaded with various catalysts, and the rational design of the electrode structure plays a crucial role in improving the reaction kinetics and energy efficiency of eCO₂RR. The purpose of this section is to clarify the characteristics and fabrication of three major types of electrodes, namely traditional non-GDEs, planar GDEs, and tubular GDEs.

3.1 Electrocatalyst integration in electrodes

Electrode electrocatalysts are an essential component of an effective electrode design, and several emerging options have been reported. In recent years, several excellent reviews have provided detailed summaries of the electrocatalysts for eCO₂RR.^{19,23,56,102,181} Therefore, in this review, the strategies for the optimization of electrode design are the major focus.

Several transition metal (e.g., Cu, Ag, and Zn) and main group metal (e.g., Bi, In, and Sn) elements, have been widely used in eCO₂RR due to their inherent CO₂ catalytic activity. The metal catalysts can be divided into four categories based on their selectivity towards the target product (the reaction pathways of different metals are described in Section 2.3), as follows: (1) Bi, In, Sn, Pb, Zn, and Hg produce mainly HCOOH/HCOO⁻; (2) Zn produces formate and CO; (3) Au and Ag lead to CO; and (4) Cu yields mainly gaseous of CO, HCHO, CH₄, and C₂H₄. In particular, Cu is the most widely studied metal catalyst because its unique electronic structure and surface chemical properties allow it to selectively generate a wide range of hydrocarbons and oxygenate products.^129,142 To improve the performances of eCO₂RR, the core task is to design and optimize the morphology and structure of the electrode material. The strategies for material development mainly include nanostructuring, oxidation state regulation, defect engineering, alloying, core–shell structure construction, doping, and surface functionalization (Fig. 6).^56,102 These strategies can improve the activity, selectivity, and stability of electrode materials by controlling the size and morphology of the catalysts, increasing the number of active sites, regulating the valence state and coordination environments of the metal active centers, and optimizing the electronic structure of metals.

3.2 Structural design of non-GDEs and planar GDEs

The traditional planar electrodes originally used for H-cells have almost been exclusively adopted for the rapid evaluation of electrocatalysts due to their simple assembly in experiments. Most state-of-the-art nano-structured electrocatalysts are powder-based materials. Therefore, the preparation of these nanoscale electrocatalyst-based electrodes is often achieved by loading the catalyst onto a substrate (e.g., glassy carbon, carbon paper, carbon cloth, metal foil, and metal foam) (Fig. 7a). The preparation of these electrodes usually begins with an ink containing a powdered catalyst, binder, and conductive additives, which help prevent the agglomeration of the particles and enhance their adhesion to the substrate. Nafion (perfluorosulfonic acid, PFSA) is a widely used binder for the preparation of electrodes in various electrochemical applications.^223–225 A variety of loading methods on a supporting conductor, such as air-brushing, drop-casting, dip-coating, and spin-coating, can be used to prepare catalyst-supported electrodes. However, the Nafion ionomer forms a proton-rich environment around the catalytic surface, which facilitates HER, and thus reduces the selectivity of the CO₂ catalyst.^26,223,226 Alternatively, the incorporation of inert components inevitably increases the CO₂ transport resistance and usually limits the catalyst loading, affecting the catalytic performance. Therefore, the development of electrodes that do not require ionomer bonding has been accepted as a promising way to further improve the performance of eCO₂RR.

Some studies have used the method of in situ growth of catalysts on a conductive substrate to prepare self-supporting electrodes (Fig. 7b).^227–229 This strategy improves the homogeneity of the loaded catalyst particles and provides a simple and scalable synthesis method to prepare the working electrodes. The in situ incorporation of nanostructured catalysts can be done via various approaches, such as solvent-thermal, template synthesis, and electrodeposition, which avoids the influence from the use of a catalyst ink. Self-supported electrodes that do not require the addition of a binder can expose a larger electrochemically active surface area, thereby providing adequate electrolyte accessibility to the active sites. In addition, the active material on this self-supporting electrode is in close contact with the conductive current collector, which not only facilitates charge transfer and mass diffusion but also exhibits high stability during eCO₂RR practical applications.^226,230

Therefore, researchers have developed conductive supports with different structures, including sheets (e.g., pure foils, porous foils, films, and carbon paper/cloth), foam, and mesh, which are collectively classified as conventional planar electrodes in this review when loaded with catalysts. The performance of eCO₂RR can be optimized by adjusting the morphology of the conductive substrate and the composition of the active material. However, in conventional H-cells, planar electrodes are typically submerged in aqueous electrolytes. Within this configuration, CO₂ molecules must first dissolve in the electrolyte before diffusing to the electrode surface (diffusion rate: 0.0016 mm² s⁻¹) over transport distances typically exceeding 50 μm (Fig. 8).²³¹ Subsequently, CO₂ undergoes adsorption, reduction, and desorption of the product at the active site. However, the mass transfer of CO₂ in conventional planar electrode configurations is severely constrained by two factors, as follows: (1) the low solubility of CO₂ in aqueous electrolytes and (2) the slow diffusion rate of dissolved CO₂ molecules in the catholyte. This leads to a severe shortage of local CO₂ concentration at the reaction interface, triggering a large mass transfer overpotential. Even the application of larger potentials (the mass-transfer overpotential), the current density is still limited to below 100 mA cm⁻², significantly restricting the reaction kinetics.^16,42,232 Therefore, designing electrocatalyst morphologies and tailoring triple-phase interfacial microenvironments to optimize gas–liquid–solid transport pathways has emerged as a critical strategy for enhancing the localized reactant concentration, and hence improving the product selectivity.

Gas diffusion electrodes (GDEs) can supply CO₂ gas directly to the electrode–electrolyte interface, thereby effectively mitigating the problem of CO₂ mass transfer and achieving an efficient gas–liquid–solid three-phase interface. GDEs were first proposed and investigated in fuel cells in 1967.⁴⁰ Inspired by the design of proton exchange membrane (PEM) fuel cells, the concept of GDE was introduced in eCO₂RR. GDE-based flow cell systems allow CO₂ to enter directly into the reaction site as a gas phase, avoiding the limitation of relying on the solubility of CO₂ in aqueous solution. As shown in Fig. 8, compared to conventional planar electrodes, the GDE significantly shortens the diffusion distance of CO₂ to the reaction interface (≈50 nm). Within flow cell configurations, GDEs enable coordinated regulation of continuous mass transport for reactants (CO₂ gas and electrolyte) and products, simultaneously increasing the local gas concentration, while enhancing the triple-phase (gas–liquid–solid) interfacial contact. These characteristics collectively increase the mass transfer rates by approximately three orders of magnitude, thereby boosting the current density for the eCO₂RR to the 1 A cm⁻² level.^41,45 It is particularly important to note that unfavourable kinetic behaviour during the product mass transfer process may lead to product accumulation on the active site surface region, causing blockage of the active sites and undesirable reduction of the product.^25,233

GDEs are typically constructed in a laminated structure, including a gas diffusion layer (GDL) and a catalyst layer.³⁹ The GDL can be either a single or dual layer, with the former referring to a GDL with a macroporous substrate, and the latter comprising both a macroporous substrate and a hydrophobic microporous layer (Fig. 7c). Generally, dual-layer GDLs are preferred because of their ability to more flexibly regulate the properties of each layer, optimizing the overall conductivity, hydrophobicity, and permeability.²³⁴ Commercial carbon-based GDLs are typically used as a porous hydrophobic support (Fig. 7d), and their macroporous substrate is usually composed of a dense carbonaceous fiber substrate, such as carbon paper and polytetrafluoroethylene (PTFE) membrane, which is used as a porous support for the catalyst layer and a current collector.²³ The microporous layer usually consists of carbon black nanoparticles (NPs) mixed with a hydrophobic polymer such as PTFE on the top of a macroporous substrate scaffold. The hydrophobic polymer contributes to the formation of a hydrophobic environment on the GDL surface, preventing the penetration of the electrolyte, and the nano-microporous structure of the microporous layer facilitates the diffusion of CO₂ molecules to the catalyst layer through the back of the GDL, while promoting the transport of the gas products into the flow field.^43,235 This architecture can effectively form a gas–electrolyte–catalyst three-phase interface, which extends the contact between CO₂ molecules and the catalyst, thereby increasing the local CO₂ concentration and facilitating electron transfer.

Typically, for the preparation of the catalyst layer, a common method is spray coating of powder-type electrocatalysts onto a GDL using ionomers or binders such as the anionic poly-sulfonic acid, cationic poly-imidazolium ionomer, polypyrrole, and Nafion (Fig. 7d).^98,240,241 This type of laminate-assembled GDE configuration supports the use of a wide range of catalysts such as heterogeneous single metals, molecular compounds, and single-metal–atom-doped carbons. Heterogeneous single metal catalysts include metal films and nanoparticles, whereas molecular compounds include metal oxides, nitrides, halides, and alloys. However, conventional GDEs with laminated structures suffer from the problem that the binder may mask their active sites and hinder gas transport. Under electrolysis conditions, the binder would undergo inevitable aging, leading to separation of the catalyst from the microporous layer, increasing the overpotential and decreasing the eCO₂RR activity.^240,242 Thus, to achieve improved eCO₂RR performances, the catalyst activity, stability, and utilization should be considered in the design of the catalyst layer. It was demonstrated that the thickness and porosity of the cathodic catalyst layer also have a significant effect on the gas mass transport, especially when the catalytic layer has a relatively porous structure, which can improve the gas–liquid mass transport process on the catalyst surface.^234,243

Refinement and optimization of the GDE configuration are aimed at achieving high commercial and industrial compatibility of eCO₂RR to produce value-added fuels and chemicals.^41,238,244 One approach is to directly deposit the catalytic layer on a hydrophobic PTFE substrate via vacuum thermal evaporation or ion sputtering technique (Fig. 7e). However, the inherent insulating nature of the PTFE material leads to low conductivity and insufficient interfacial stability in the GDE. If the target catalytic layer has good electrical conductivity (e.g., conductive metal film), no additional microporous layer support is required.^43,234 Therefore, it would be highly desirable to merge the laminated catalytic layer, macroporous substrate, and microporous layer into one integrated structural design. Recently, integrated GDEs have been fabricated via the in situ growth of catalysts on GDLs (including conductive substrates and hydrophobic microporous layers) through methods such as solvent-thermal reaction,²⁴⁵ electron beam evaporation,²⁴⁶ electrodeposition,²⁴⁷ and electrospinning technique.⁴³ This integrated approach would greatly simplify the fabrication process, expose more active sites, and bypass the effects from adding binders. This overall GDE configuration not only has improved chemical stability and mechanical properties, but also accelerates the CO₂ mass transport and electron transfer.

However, although some GDEs with improved architectures can vastly increase the current density and Faraday efficiency,^248,249 their poor production yield, operational stability, and energy efficiency in H-type and flow cells remain challenges.^250–253 GDE surfaces that lack sufficient hydrophobicity may be penetrated by water or electrolyte into the GDL pores, leading to flooding phenomena, while some impurities may cover the catalyst active sites, hindering the diffusion of CO₂ to the catalyst, and consequently causing stability issues.⁴³ Therefore, regulating the wettability of GDE surfaces is a key strategy to ensure the long-term stable operation of electrolysis systems. The long-term hydrophobicity of GDEs can be improved by adding specific hydrophobic components or constructing superhydrophobic micro/nanostructured hierarchical structures.^{99,226,239,254} Specifically, novel GDEs with hierarchical porosity have been developed to construct hydrophilic–hydrophobic nanochannels in the catalytic layer (Fig. 7f), where robust superhydrophobic GDEs can effectively resist electrolyte penetration and maintain a stable three-phase interface and microenvironment, thereby maintaining stable selectivity for the formation of the target product.^82,239

Although planar GDEs have witnessed remarkable progress, there are still a few main issues that need to be addressed. Currently, the majority of GDEs utilize commercially available GDLs with standardized characteristics, making it difficult to regulate their porosity and hydrophobicity.^237,255 It is worth noting that constructing GDEs with long-term hydrophobicity is critical, especially for stable operation at large industrial-level current densities.^84,239 In addition, planar GDEs suffer from a failure mode due to carbonate/carbonate salt contamination in flow cells, which causes CO₂ loss and aggravates the instability of the electrode configuration, thereby limiting the CO₂ conversion and energy efficiency.^23,39,84,256 Furthermore, the effective surface area of planar GDEs is limited by the size of the reactor, and more GDEs need to be assembled to increase the active specific surface area to meet industrial applications.²⁵⁷ Therefore, the design of novel electrode configurations with simplified and highly stable structures will facilitate the reactor design.

3.3 Structural design and techniques for the fabrication of microtubular GDEs

4. Recent advances in upgraded electrode structures in eCO₂RR

The electrode is considered a key component of eCO₂RR, which has the function of supporting the catalyst and mass transfer. Therefore, the performance of eCO₂RR is highly dependent on the electrode assembly, which includes not only the development of catalysts but also the design of electrodes with improved structures. A well-designed electrode structure can maximize the active sites of the catalyst and help prevent particle agglomeration, thereby improving the overall efficiency of eCO₂RR. Thus, advanced structure electrodes are of great significance in achieving the commercial large-scale application of eCO₂RR; however, the structure of the electrode is often overlooked.^45,311,312 Here, we review the state-of-the-art progress in conventional non-GDEs, planar GDEs, and microtubular GDEs, as well as explore their potential for application in eCO₂RR.

4.1 Conventional non-GDE structures

With the rapid development of nanomaterials and nanotechnology, electrocatalysts based on conventional electrodes have been extensively explored, and a variety of electrode electrocatalysts for eCO₂RR with considerable efficiency and selectivity have been developed and reviewed.^{16,23,102,313} Apart from the electrocatalyst layer, the structural design of electrodes is also a critical aspect for achieving highly efficient eCO₂RR and requires further attention.^82,128,311 However, the conventional electrodes in H-cells need to be fully immersed in the cathode solution during operation, while CO₂ is usually introduced into the electrolyte by continuous bubbling, and then diffuses to the electrode surface. This makes the diffusion/adsorption of CO₂ molecules and desorption of the products on the electrocatalyst surface the rate-limiting step affecting the catalytic performance.^250,314 This section focuses on the structure of conventional non-GDEs to inform the design of electrodes for industrial applications in the future. According to the architecture of conventional non-GDEs, they mainly include bulky metal electrodes, powder-based electrodes, and self-supported electrodes.

4.2 Advanced planar GDE structures

Gas diffusion electrodes (GDEs) are emerging as an electrode configuration designed to overcome the limitations of CO₂ mass transfer (Fig. 15). A key difference between planar GDEs and conventional non-GDE configurations is the contact mode between CO₂ and the electrolyte.³⁶⁰ Planar GDE electrochemical flow cell systems can deliver CO₂ directly through the gas diffusion layer (GDL) to the catalyst layer, allowing it to reach the active sites on the catalyst surface quickly and under short diffusion distances, thereby significantly enhancing the CO₂ mass transfer. In addition, the combination of planar GDEs with flow cells or membrane electrode assemblies (MEAs) greatly facilitates the gas mass transfer and improves the current density, which provides strong support for the practical process of eCO₂RR. Therefore, planar GDEs with advanced structure design have a broad application prospect in the eCO₂RR.

In this section, we focus on the latest structural designs of planar GDEs, including laminated GDEs, integrated GDEs, free-standing GDEs, and tandem electrodes, as well as discussing the state-of-the-art performances and challenges associated with these electrode designs.

4.3 Microtubular GDE structures

The electrode material, morphology, defect location, surface properties, and electronic structure can significantly affect the activity and product selectivity. Compared with planar GDEs, microtubular GDEs show unique features due to their self-supporting porous structure and gas permeability properties.^165,442 These electrodes with a spatial structure are typically composed of a single active metal without the need for any additive, binder, or substrate assembly, which leads to improved continuity of electron transfer, reduced ohmic losses, and enhanced structural integrity.^53,128,443 In the eCO₂RR process, these electrodes with hollow structures compel CO₂ to penetrate the porous cross-section and reach the active site to participate in the reaction instead of diffusion in the planar electrode.⁴⁴² The CO₂-disperser mode induces the in situ formation of a large number of gas–liquid–solid three-phase interfaces, which significantly improves the reaction kinetics and the mass transport efficiency of CO₂, protons, and products.²⁶⁰ Meanwhile, the presence of a pressure drop effectively prevents electrolyte flooding, and thus the selectivity and stability can be well maintained even under high current density.²⁸⁶ This section focuses on the recent advances in the design of microtubular GDEs, mainly including monometallic-type, bimetallic-type, and other modified structures of electrodes.

4.4 (Bi)carbonate formation and its impact on electrode performance

Durable electrode designs improve the eCO₂RR performance and stability of the electrolysis system. Although hydrophobicity has been optimized in numerous studies, another key issue affecting the long-term operation stability is the presence of carbonate precipitation.

Alkaline electrolytes can inhibit HER and achieve highly selective eCO₂RR products. However, the rapid consumption of H⁺ during electrolysis creates a local alkaline environment in the cathodic catalytic layer, resulting in the input CO₂ reacting mainly with OH⁻ to form CO₃²⁻/HCO₃⁻ (eqn (10) and (11)), rather than being reduced, as presented in Fig. 30.^39,91 This phenomenon is particularly evident during steady-state electrolysis at a high current density, where a large amount of carbonates is precipitated on the GDE surface. This accumulation of carbonates blocks the active sites and hinders CO₂ transfer, ultimately leading to the complete blockage of the GDE microporous layer.^66,97 In addition, CO₃²⁻ can be transferred from the cathode to the anode as a charge carrier and OH⁻ in a CO₂ electrolyzer assembled with an anion exchange membrane (AEM). At the anode, they can be oxidized to CO₂/O₂ (eqn (12) and (13)), resulting in the crossover of CO₂ with produced O₂. This process induces significant CO₂ losses, and consequently reduces both the SPCE and stability of the eCO₂RR, ultimately limiting its practical application.^25,256

Due to these problems in alkaline electrolytes, researchers have turned to neutral/acidic electrolytes. For example, neutral electrolytes such as KHCO₃ have pH buffer capacity and can directly react with OH⁻ or H⁺ to buffer the local pH microenvironment, which can contribute to enhanced performance stability of the eCO₂RR process.^391,474,475 Recently, Liu et al. showed that a GDE with a low-porosity catalytic layer hinders the diffusion of HCO₃⁻ and weakens the pH buffer effect. In contrast, a catalytic layer with high porosity significantly promotes the efficient mass transfer of HCO₃⁻ and local OH⁻, while also and enhancing the pH buffer capacity. This ensures a continuous supply of H⁺ and maintains the optimal CO₂ concentration, thereby supporting sustained catalytic reaction.⁴⁰³ However, the high resistance in neutral electrolytes limits its practical application. Another feasible strategy is conducting eCO₂RR in acidic media. Low pH cathode electrolytes effectively inhibit (bi)carbonate formation and crossover, but this proton-rich environment makes HER kinetically superior to eCO₂RR.^93,476 By periodically adding HCl to the KCl catholyte, the increased pH is effectively compensated and the accumulation of (bi)carbonate is eliminated. This approach enables sustained C₂H₄ selectivity at a current density of 150 mA cm⁻² for 30 h, superior to the case without HCl addition, where the pH of the catholyte rises to 10.6 after only 12 h reaction.³⁹¹

Recent studies have shown that infusing high concentrations of alkali cation solution into the acidic catholyte can inhibit the competing HER.^39,361 Alkali cations (e.g., K and Cs) not only effectively shield the electric field in the diffusion layer, but also modulate the electrostatic interaction and generate an enhanced local electric field to stabilize the eCO₂RR intermediates. Meanwhile, physisorbed alkali cations can also inhibit the migration of cationic hydronium ions to the electrode surface, and thereby weaken the HER. However, a high concentration of alkali cations can also lead to the accumulation of carbonate precipitates on the GDE surface.^448,477,478 Janaky et al. achieved a CO partial current density of 420 ± 50 mA cm⁻² at 3.2 V vs. RHE, stable electrolysis for more than 200 h, and FE_CO of 90% for an Ag GDE by employing this strategy.⁴⁷⁸ Another strategy to mitigate carbonate precipitation is by temporarily and periodically reducing the applied voltage. This strategy reduces the concentration of alkali metal cations near the cathode by their intermittent diffusion, while maintaining negative polarization at the cathode to transport CO₃²⁻ to the anode under an electric field.³⁸⁸ Employing this self-cleaning strategy, a Cu-PTFE GDE could be operated stably for 157 h (total duration 236 h).⁹⁶

In addition, carbonate formation and crossover during eCO₂RR can be effectively suppressed by assembling a flow cell with a cation exchange membrane (CEM) and a bipolar membrane (BPM).^388,479 In acidic electrolytes, CEM effectively mitigates (bi)carbonate accumulation and CO₂ crossover to the anode through proton transfer. However, although this increases the rate of eCO₂RR, it simultaneously promotes HER.³⁶¹ The outward diffusion of H⁺ and OH⁻ produced in BPM can inhibit the crossover of anions and neutral products.⁴⁸⁰ Flow cells with BPM exhibit higher activity and durability compared to CEM- and AEM-based flow cells.^66,92 However, the larger membrane potential of the BPM under a reverse bias leads to an increase in the overpotential to drive CO₂ electrolysis, reducing the energy efficiency of the overall flow cell.^73,361 This is the main drawback preventing the large-scale application of BPMs. Although the above-mentioned strategies alleviate the problem of carbonate formation and crossover in GDEs to a certain extent, achieving industrially applicable stability of the electrolysis system remains an urgent challenge yet to be solved.

CO2 + OH− → HCO3−	(10)

CO2 + 2OH− → CO32− + H2O	(11)

2CO32− → 2CO2 + O2 + 4e−	(12)

2OH− → 2H+ + O2 + 4e−	(13)

5. Conclusions and perspectives

Electrocatalytic CO₂ reduction to high-value fuels and chemicals is progressively moving from laboratory research to industrial applications as an attractive pathway for CO₂ utilization. Considering the increasing emphasis on high economic efficiency and environmental demands, eCO₂RR technology is transforming from exploration under low-current conditions to high current densities as required by industrial applications.^313,388 As discussed in this review, the electrodes, as key components of the eCO₂RR system, determine the performance of the electrolyzer. Thus, the design of advanced electrode configurations and the establishment of electrode interface reaction mechanisms are needed to improve the stability and selectivity at high currents.

Despite the progress in catalyst design for conventional non-GDEs, the performance of these electrodes in H-cells is limited by CO₂ diffusion in the bulk electrolyte, whose low solubility and slow mass transport result in a limited current density (≤100 mA cm⁻²) and stability (≤50 h). These limitations hinder their large-scale production and industrial application. In contrast, planar GDEs in flow cells have been designed to effectively overcome mass transport limitations, including the optimization of laminated, integrated, 3D free-standing and tandem electrode configurations. Improved current densities of >1 A cm⁻² have been reported with ≥100 h stable operation. These electrode structures can be effectively scaled to larger stacks for industrial scale-up. However, the stability of the reactor faces challenges in the flow cell due to the susceptibility of GDEs to electrolyte flooding and (bi)carbonate formation. Microtubular GDEs or GPEs (gas penetration electrodes) are the latest electrode configuration with a unique gas transport mode that effectively enhances CO₂ mass transfer and expands the three-phase reaction interface. The electrode structure can be further optimized by modulating the porosity, wall thickness, component, and surface characteristic. Microtubular GDEs have achieved maximum current densities of up to 4 A cm⁻² and 85% SPCE with stability of ≥200 h.⁹³ These electrodes with a compact structure not only effectively prevent flooding, but also demonstrate appropriate scalability by expanding into electrode arrays, which show promising potential for the practical application of eCO₂RR.²⁵⁷

However, although more encouraging large-current models have been obtained via rational modulation of the electrode configurations,^{45,100,414,481} the applied research for industrial transformation still deserves further consideration. The following are some recommendations for future studies on electrodes.

(1) Increasing partial current density and selectivity. Significant advancements have been made in the activity and selectivity of CO₂ conversion to products such as CO, HCOOH, and C₂H₅OH over the past decade, with planar and microtubular GDEs demonstrating remarkable performances. However, maintaining these laboratory-scale metrics during industrial-scale amplification remains challenging, necessitating novel strategies to boost the intrinsic activity for commercial implementation. Dual/multi-site synergistic design (e.g., quinary high-entropy alloys) is a promising approach, wherein differentiated metal electronic structures precisely regulate the key intermediates, thereby optimizing the reaction pathways and product selectivity.^482,483 Upgrading the electrode structure is equally critical. For example, hierarchical porosity, substrate-free freestanding membrane electrodes, and gradient hydrophobic architecture designs can improve the local CO₂ concentration and active surface area.^45,239 Microtubular GDEs can perform multiple functions, including catalysis, gas distribution, and structural support, and particularly their multi-channel configuration is expected to enhance the mass transfer efficiency at the three-phase interface.^484,485 In addition, how some core components (e.g., catalyst layer, substrate layer, polymer and membrane, and electrolyte) affect the electrode reaction interface under industry-related conditions is still elusive. In particular, the formation of multi-carbon products involves complex multiple couples of proton–electron transfer and C–C coupling steps. Therefore, we recommend deploying in situ characterization techniques to observe and track the intermediate behaviors and interfacial dynamics during eCO₂RR. Establishing clear interface structure-performance relationships will guide the reaction pathways of the target products.

(2) Improving high-current stability. Currently, only a few GDE-based MEAs are capable of continuous operation of >1000 h for C₁ products, while the typical operation cycle reported in the literature remains limited to ∼200 h for C₂₊ products. Also, although planar and microtubular GDEs enable high current density CO₂ conversion to C₂₊, their long-term stability remains a core challenge for industrialization. Thus, the electrode design must balance activity with stability, particularly given that the cathode failure modes (e.g., catalyst degradation, electrode structural collapse, flooding, and carbonate precipitation) are exacerbated during the durable operation at high currents, accelerating the aging of the reactor.

To address these challenges, we recommend that advanced in situ electrochemical diagnostics with high spatiotemporal resolution, coupled with accelerated stress testing be employed to investigate the electrode failure mechanisms and advance durable electrode designs.^486,487 Meanwhile, developing analytical theoretical calculations and multi-physics field simulations is imperative for the rapid screening of stable catalytic materials and reasonable assessment of the reaction kinetics.^23,488,489 Furthermore, the rational design of hierarchically ordered electrode architectures can optimize the mass transport channels, while enhancing the operational durability. Notably, all-solid-state systems integrating microtubular GDEs with polymer electrolytes show significant potential for mitigating flooding and salt deposition.^490,491 Consequently, future research should prioritize extending the electrode longevity under industrial current densities through holistic optimization ranging from catalyst development to electrode and reactor integration, ultimately advancing scalable eCO₂RR electrolysis technologies for practical implementation.

(3) Enhancing energy efficiency and carbon efficiency. As a core parameter determining the techno-economic viability of CO₂ reduction, a standardized evaluation system is urgently needed for the optimization of the system energy efficiency (EE). Current studies have mostly focused on performance metrics such as FE and current density, but have neglected the critical impact of full-cell voltage on EE under steady-state operating conditions. It is worth noting that a high FE and current density are often accompanied by elevated overpotentials, which paradoxically result in a decreased overall EE, and ultimately compromised economic benefit. This suggests that future investigations should focus on breakthroughs in low-overpotential operation techniques under steady-state conditions at high current densities.

Carbonate formation not only exacerbates the energy consumption but also reduces the carbon efficiency, thereby hindering the transformation of industrial applications for eCO₂RR, especially in multicarbon product synthesis.^83,179,492 Collaborative suppression strategies include implementing alkali-cation-free electrolytes, designing highly conductivity membranes, and modulating the cathode microenvironment by optimizing the local pH at the cathode and narrowing the gap between the electrode and membrane.^23,493–495 Concurrently, innovations in electrode and reactor design will control the product separation costs. For example, selective ion-exchange membranes effectively block specific product crossover. The novel microtubular GDEs have attracted attention owing to their unique three-dimensional porous architecture and permeation effect to accelerate CO₂ mass transport and enhance triple-phase interface reactions, thereby substantially improving both the energy and carbon efficiency.^496,497 This development of advanced electrodes is expected to achieve high production efficiency at ampere-level current densities for eCO₂RR, demonstrating large-scale industrial application potentials. Moreover, well-designed cascade reactor systems can effectively address core issues (e.g., salt deposition and CO₂ crossover) via step control of single electrodes, thereby improving the conversion efficiency and stability.^120,141 Therefore, future eCO₂RR development should focus on the cascade integration of various devices to achieve major breakthroughs in industrial performance and product diversity.

(4) Addressing primary cathode failure modes in CO₂ electrolysis systems. Industrial CO₂ electrolysis systems operating at high current densities face core critical failure modes including (bi)carbonate deposition, frequent flooding, CO₂ crossover, and competitive HER. These issues severely constrain the core performance metrics by reducing the active site availability and impeding the mass transport efficiency.

In terms of (bi)carbonate deposition, the strongly alkaline microenvironment induced by high current densities promotes carbonate formation, which blocks the active sites and impedes CO₂ diffusion. Currently, the formation of (bi)carbonates is suppressed through electrolyte engineering (e.g., low pH cathode electrolytes or alkali metal cations-free polymer electrolytes), and a potential regulation scheme is employed to facilitate the diffusion of alkali metal cations by temporarily and periodically reducing the applied voltage.^141,498 However, these proton-rich environments risk exacerbating the HER competition. Furthermore, to address the electrode instability caused by salt deposition in the cathode chamber, recent research has proposed a novel strategy of introducing trace amounts of volatile acid vapor into the CO₂ input stream. This approach maintains unobstructed CO₂ flow channels by enhancing the salt solubility and suppressing (bi)carbonate crystallization. Compared to conventional water humidification methods, acid-humidification regulation significantly enhances the electrode operational stability (up to 4500 h), while preserving the reaction selectivity and cell voltage.⁴⁹⁹

Electrode flooding arises from electrolyte penetration, which restricts CO₂ transport. Flooding essentially differs from salt precipitation by inducing structural degradation in the GDE layers through complex multifactorial pathways. The binder and carbonaceous materials are prone to oxidative degradation during the reaction process, leading to electrode structural collapse.³²⁰ On the other hand, local accumulation of (bi)carbonate affects the surface wettability of the electrode during testing.⁵⁰⁰ Thus, effective countermeasures require optimizing the intermediate adsorption/desorption kinetics, while developing corrosion-resistant materials. Concurrently, engineered architectures, including hierarchically porous structures, micro/nano-structured hydrophobic layers, superhydrophobic freestanding electrodes, and microtubular electrode designs, enhance the flood resistance. Moreover, liquid-free electrolysis systems also offer promising alternatives.

Similar to salting-out reactions, especially at high current densities, (bi)carbonate ions formed at the cathode–electrolyte interface migrate to the anode under an electric field, recombining into CO₂, which contaminates the anodic O₂.³⁸⁸ This necessitates novel ion-selective exchange membranes and flow cell configurations to minimize the carbon losses.⁵⁰¹

The competing HER is considered one of the main factors leading to a decrease in the FE of eCO₂RR. Thus, by modifying the electrolyte to suppress the competing HER, the selectivity of eCO₂RR for producing hydrocarbon products can be improved. Introducing high-charge-density cationic polymers electrostatically impedes proton migration.⁴⁹⁸ Halide ion additives can the block HER-active sites and improve the local coverage of the CO₂ reduction intermediates.⁵⁰² Strategic optimization of the electrolyte concentration can simultaneously restrict proton mass transport (without limiting the CO₂ flux), thereby synergistically enhancing the activity and FE for eCO₂RR.^177,179 Furthermore, the use of appropriate selective electrode materials is considered to be the most straightforward approach.

(5) Advancing practical application environment. Although current eCO₂RR research is typically operated under ideal reaction conditions, such as high-purity CO₂, highly acidic or alkaline electrolytes, and nontoxic media, industrial deployment demands stable operation in more practical settings. Furthermore, many laboratory-scale studies still rely on high-concentration CO₂ inputs to achieve high current densities, and this approach often compromises the techno-economic viability, thus hindering the broader adoption of low-temperature CO₂ electrolysis technology. In contrast, practical CO₂ sources such as typical industrial flue gases present a more complex challenge due to their low CO₂ concentrations and multi-component nature. Therefore, it is necessary to establish a robust electrolysis mechanism capable of efficiently handling low-purity CO₂ streams.⁵⁰³ Integrating upstream carbon capture with downstream product separation offers a promising route toward energy-optimized, closed-loop carbon cycles.⁵⁰⁴ In addition, achieving high-current eCO₂RR by directly converting flue gas has become a central focus of current research. Nevertheless, coexisting toxic components such as SO_x and NO_x can poison the active sites, necessitating specifically tailored electrode architectures and active components to counteract these toxins.^505,506 By optimizing the substrate, the electrode can be engineered to obtain excellent corrosion resistance in practical operating environments. Modifying GDEs with porous carbons and metal–organic frameworks can increase the local CO₂ availability at the electrode surface due to their superior CO₂ adsorption ability.^507–509 Furthermore, ionomer-modified GDEs not only increase the local CO₂ concentration but also protect the reactive sites from deactivation due to poisoning by impurities in the flue gas.^415,510 Consuming CO₂ and generating value-added products via direct flue gas electrolysis can offer economic interest. Consequently, future efforts should focus on high-current CO₂ conversion under low-concentration CO₂ conditions to simulate more reliable industrial environments and improve the economic viability.

In summary, breakthroughs in electrode design represent a crucial prerequisite for advancing eCO₂RR technology toward industrialization. Although significant challenges remain in efficiently converting CO₂ into value-added chemicals and fuels, from basic research to industrial application, recent innovations in electrode configurations, material systems, and characterization techniques have laid a robust foundation for progress. Future efforts should focus on continuously optimizing electrolysis systems by enhancing the material stability, refining electrode structures, and improving the electrolyzer configurations, alongside establishing precise in situ characterization methods and deepening our understanding of the reaction mechanisms. Collectively, these efforts will effectively accelerate the translation of eCO₂RR technology from laboratory-scale experiments to industrial applications, contributing meaningfully to the sustainable development of the global carbon cycle.

Author contributions

Xiaofeng Ke: conceptualization, formal analysis, visualization, writing – original draft. Weicong Xu: resources, investigation. Chao Liu: collaboratively designed and corrected the figures. Yakun Wang: writing – review & editing. Xiaozhong Huang: writing – review & editing. Rui Xiao: supervision, writing – review & editing. Xiaomin Xu: conceptualization and writing – review & editing. Tao Li: project administration, funding acquisition, supervision and writing – review & editing. Zongping Shao: supervision, validation and writing – review & editing.

Conflicts of interest

The authors declare no conflict of interest.

Data availability

No primary research results, software or code has been included and no new data were generated or analysed as part of this review.

Acknowledgements

This work was financially supported by the National Key R&D Program of China (2022YFB4004000), the National Natural Science Foundation of China (U24A20542, 52276175), and Fundamental Research Funds for the Central Universities (501xTCX2023146001).

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