Nanoscale Management of CO Transport in CO2 Electroreduction: Boosting Faradaic Efficiency to Multicarbon Products via Nanostructured Tandem Electrocatalysts

Tandem catalysis presents a promising strategy to improve the selectivity toward multicarbon products in the electrocatalytic carbon dioxide reduction reaction (CO₂RR). For CO₂RR, CO is a critical intermediate for producing multicarbon products. However, the management of CO localization and CO diffusion remains underexplored despite its critical role. Herein, a 3D tandem catalyst electrode with silver nanoparticles (Ag NPs) is designed to generate CO as an intermediate product within a copper (Cu) nanoneedle array. Via this nanostructured design, CO₂ forms C²⁺ products with a high Faradaic efficiency (FEC²⁺) of 64% in an H-cell and 70% in a flow cell with a current density of 350 mA cm⁻². These figures-of-merit are currently among the top literature reports. More importantly, in situ Raman spectroscopy and finite-element method calculations are employed to elucidate the origins of enhanced selectivity. These approaches reveal the crucial role of prolonging the CO diffusion path length for improving CO utilization during CO₂ conversion with tandem catalyst systems. The favorable CO2RR FEC²⁺ in two distinct environments (H-cell and flow cell) further corroborates that this effect is not limited to a particular reactor environment. Overall, this study provides new insights for designing tandem catalysts for improved CO₂RR selectivity to C²⁺ products.     

Accelerating Proton and Electron Transfer Enables Highly Active Fe─N─C Catalyst for Electrochemical CO2 Reduction

Atomically dispersed Fe─N─C catalysts display great potential for efficient CO production in the field of electrochemical CO₂ reduction (ECR), but still suffer from unsatisfactory activity limited by the slow proton and electron transfer during the ECR process. Here, a superior Fe─N─C electrocatalyst is designed by anchoring the individual FeN₄ sites and Fe nanoparticles onto highly conductive carbon nanotubes. The resultant catalyst displays a commendable CO partial current density of 16.01 mA cm⁻² with a turnover frequency of 3519.6 h⁻¹ at −0.65 V in an H-type cell, and also exhibits CO selectivity > 90% under high current density over 120 mA cm⁻² in a flow cell. This remarkable activity exceeds a host of previously reported Fe─N─C catalysts. The findings indicate that the carbon nanotube facilitates CO production due to its strong capability of electron transport and charge transfer. In situ spectroscopic analysis, controlled experiments, and theoretical calculations reveal that Fe nanoparticles effectively promote water dissociation and the subsequent protonation step, accelerate the formation of ^*COOH intermediate, and thus greatly enhance the ECR activity.     

Selenium‐Doped Hierarchically Porous Carbon Nanosheets as an Efficient Metal‐Free Electrocatalyst for CO2 Reduction

Electrochemical carbon dioxide reduction reaction (CO₂RR) provides a promising pathway for both decreasing atmospheric CO₂ concentration and producing valuable carbon‐based fuels. To explore efficient and cost‐effective catalysts for electrochemical CO₂RR is of great importance, but remains challenging. Se‐doped carbon nanosheets (Se‐CNs) with a micro‐, meso‐, and macroporous structure are proposed for electrochemical CO₂RR. Such an electrocatalyst combines the advantages of Se optimized active sites, hierarchical pores for facilitating reactant or ion penetration, transport and reaction, and large surface area for more accessible active sites. This Se‐CNs electrocatalyst exhibits over 11‐times enhanced partial current density of CO than the CNs without Se doping and high selectivity (90%) for CO₂ electroreduction to CO at a low potential of ?0.6 V versus the reversible hydrogen electrode (vs RHE). Density function theoretical calculations reveal that the Se introduction in CNs lowers the free energy barrier of CO₂RR and inhibits hydrogen evolution reaction effectively, thus improving the selectivity for CO₂ reduction to CO. This work presents a new member of the metal‐free electrocatalyst family, which is easily prepared, low cost, adjustable, and highly efficient for CO₂RR.     

Identifying Active Sites of Nitrogen‐Doped Carbon Materials for the CO2 Reduction Reaction

Nitrogen‐doped carbon materials are proposed as promising electrocatalysts for the carbon dioxide reduction reaction (CRR), which is essential for renewable energy conversion and environmental remediation. Unfortunately, the unclear cognition on the CRR active site (or sites) hinders further development of high‐performance electrocatalysts. Herein, a series of 3D nitrogen‐doped graphene nanoribbon networks (N‐GRW) with tunable nitrogen dopants are designed to unravel the site‐dependent CRR activity/selectivity. The N‐GRW catalyst exhibits superior CO₂ electrochemical reduction activity, reaching a specific current of 15.4 A g_catalyst^?1 with CO Faradaic efficiency of 87.6% at a mild overpotential of 0.49 V. Based on X‐ray photoelectron spectroscopy measurements, it is experimentally demonstrated that the pyridinic N site in N‐GRW serves as the active site for CRR. In addition, the Gibbs free energy calculated by density functional theory further illustrates the pyridinic N as a more favorable site for the CO₂ adsorption, *COOH formation, and *CO removal in CO₂ reduction.     

Hierarchical Ni/N/C Single-Site Catalyst Achieving Industrial-Level Current Density and Ultra-Wide Potential Plateau of High CO Faradic Efficiency for CO2 Electroreduction

The practical applications of CO₂ electroreduction to CO driven by renewable electricity should simultaneously meet the requests of industrial-level CO partial current density (J_CO) at least 100 mA cm⁻², wide potential window of high CO faradic efficiency (FE_CO), and low cost. Herein, a new strategy is reported to construct porous hierarchical Ni/N/C single-site catalyst with excellent catalytic activity via coating Ni-containing ZIF-8 on mesostructured basic magnesium carbonate template followed by pyrolysis. The abundant micropores facilitate the formation of numerous edge-hosted Ni-N₄ sites with high intrinsic activity, and the interconnected macro/mesopores much promote CO₂ delivery and CO release for the full expression of intrinsic activity. Consequently, the catalyst exhibits the industrial-level J_CO of 105–462 mA cm⁻² at the potential range of −0.6∼−1.3 V with ultra-wide high FE_CO plateau (>90%@−0.4∼−1.3 V), showing great promise for practical application. This study provides a general synthetic strategy to explore high-performance hierarchical M/N/C electrocatalysts.     

N‐Doped Polypyrrole‐Based Porous Carbons for CO2 Capture

Highly porous N‐doped carbons have been successfully prepared by using KOH as activating agent and polypyrrole (PPy) as carbon precursor. These materials were investigated as sorbents for CO₂ capture. The activation process was carried out under severe (KOH/PPy = 4) or mild (KOH/PPy = 2) activation conditions at different temperatures in the 600–800 °C range. Mildly activated carbons have two important characteristics: i) they contain a large number of nitrogen functional groups (up to 10.1 wt% N) identified as pyridonic‐N with a small proportion of pyridinic‐N groups, and ii) they exhibit, in relation to the carbons prepared with KOH/PPy = 4, narrower micropore sizes. The combination of both of these properties explains the large CO₂ adsorption capacities of mildly activated carbon. In particular, a very high CO₂ adsorption uptake of 6.2 mmol·g^?1 (0 °C) was achieved for porous carbons prepared with KOH/PPy = 2 and 600 °C (1700 m²·g^?1, pore size ≈ 1 nm and 10.1 wt% N). Furthermore, we observed that these porous carbons exhibit high CO₂ adsorption rates, a good selectivity for CO₂‐N₂ separation and it can be easily regenerated.     

Boosting Industrial-Level CO2 Electroreduction of N-Doped Carbon Nanofibers with Confined Tin-Nitrogen Active Sites via Accelerating Proton Transport Kinetics

The development of highly efficient robust electrocatalysts with low overpotential and industrial-level current density is of great significance for CO₂ electroreduction (CO₂ER), however the low proton transport rate during the CO₂ER remains a challenge. Herein, a porous N-doped carbon nanofiber confined with tin-nitrogen sites (Sn/NCNFs) catalyst is developed, which is prepared through an integrated electrospinning and pyrolysis strategy. The optimized Sn/NCNFs catalyst exhibits an outstanding CO₂ER activity with the maximum CO FE of 96.5%, low onset potential of −0.3 V, and small Tafel slope of 68.8 mV dec⁻¹. In a flow cell, an industrial-level CO partial current density of 100.6 mA cm⁻² is achieved. In situ spectroscopic analysis unveil the isolated Sn N site acted as active center for accelerating water dissociation and subsequent proton transport process, thus promoting the formation of intermediate *COOH in the rate-determining step for CO₂ER. Theoretical calculations validate pyrrolic N atom adjacent to the Sn N active species assisted reducing the energy barrier for *COOH formation, thus boosting the CO₂ER kinetics. A Zn-CO₂ battery is designed with the cathode of Sn/NCNFs, which delivers a maximum power density of 1.38 mW cm⁻² and long-term stability.     

1D SnO2 with Wire‐in‐Tube Architectures for Highly Selective Electrochemical Reduction of CO2 to C1 Products

Electrochemical reduction of CO₂ (ERC) into useful products, such as formic acid and carbon monoxide, is a fascinating approach for CO₂ fixation as well as energy storage. Sn‐based materials are attractive catalysts for highly selective ERC into C₁ products (including HCOOH and CO), but still suffer from high overpotential, low current density, and poor stability. Here, One‐dimensional (1D) SnO₂ with wire‐in‐tube (WIT) structure is synthesized and shows superior selectivity for C₁ products. Using the WIT SnO₂ as the ERC catalyst, very high Faradaic efficiency of C₁ products (>90%) can be achieved at a wide potential range from ?0.89 to ?1.29 V versus RHE, thus substantially suppressing the hydrogen evolution reaction. The electrocatalyst also exhibits excellent long‐term stability. The improved catalytic activity of the WIT SnO₂ over the commercial SnO₂ nanoparticle indicates that higher surface area and large number of grain boundaries can effectively enhance the ERC activity. Synthesized via a facile and low‐cost electrospinning technology, the reduced WIT SnO₂ can serve as a promising electrocatalyst for efficient CO₂ to C₁ products conversion.     

Atomically Defined Undercoordinated Active Sites for Highly Efficient CO2 Electroreduction

Electrocatalytic reduction of carbon dioxide (CO₂ER) in rechargeable Zn–CO₂ battery still remains a great challenge. Herein, a highly efficient CO₂ER electrocatalyst composed of coordinatively unsaturated single‐atom copper coordinated with nitrogen sites anchored into graphene matrix (Cu–N₂/GN) is reported. Benefitting from the unsaturated coordination environment and atomic dispersion, the ultrathin Cu–N₂/GN nanosheets exhibit a high CO₂ER activity and selectivity for CO production with an onset potential of ?0.33 V and the maximum Faradaic efficiency of 81% at a low potential of ?0.50 V, superior to the previously reported atomically dispersed Cu–N anchored on carbon materials. Experimental results manifest the highly exposed and atomically dispersed Cu–N₂ active sites in graphene framework where the Cu species are coordinated by two N atoms. Theoretical calculations demonstrate that the optimized reaction free energy for Cu–N₂ sites to capture CO₂ promote the adsorption of CO₂ molecules on Cu–N₂ sites; meanwhile, the short bond lengths of Cu–N₂ sites accelerate the electron transfer from Cu–N₂ sites to *CO₂, thus efficiently boosting the *COOH generation and CO₂ER performance. A designed rechargeable Zn–CO₂ battery with Cu–N₂/GN nanosheets deliver a peak power density of 0.6 mW cm^?2, and the charge process of battery can be driven by natural solar energy.     

Hybrid Catalyst Coupling Zn Single Atoms and CuNx Clusters for Synergetic Catalytic Reduction of CO2

Reverse water-gas shift (RWGS) reaction is the initial and necessary step of CO₂ hydrogenation to high value-added products, and regulating the selectivity of CO is still a fundamental challenge. In the present study, an efficient catalyst (CuZnN_x@C-N) composed by Zn single atoms and Cu clusters stabilized by nitrogen sites is reported. It contains saturated four-coordinate Zn-N₄ sites and low valence CuN_x clusters. Monodisperse Zn induces the aggregation of pyridinic N to form Zn-N₄ and N₄ structures, which show strong Lewis basicity and has strong adsorption for *CO₂ and *COOH intermediates, but weak adsorption for *CO, thus greatly improves the CO₂ conversion and CO selectivity. The catalyst calcined at 700 °C exhibits the highest CO₂ conversion of 43.6% under atmospheric pressure, which is 18.33 times of Cu-ZnO and close to the thermodynamic equilibrium conversion rate (49.9%) of CO₂. In the catalytic process, CuN_x not only adsorbs and activates H₂, but also cooperates with the adjacent Zn-N₄ and N₄ structures to jointly activate CO₂ molecules and further promotes the hydrogenation of CO₂. This synergistic mechanism will provide new insights for developing efficient hydrogenation catalysts.     

Nitrogen Vacancy Induced Coordinative Reconstruction of Single-Atom Ni Catalyst for Efficient Electrochemical CO2 Reduction

Transition metal nitrogen carbon based single-atom catalysts (SACs) have exhibited superior activity and selectivity for CO₂ electroreduction to CO. A favorable local nitrogen coordination environment is key to construct efficient metal-N moieties. Here, a facile plasma-assisted and nitrogen vacancy (NV) induced coordinative reconstruction strategy is reported for this purpose. Under continuous plasma striking, the preformed pentagon pyrrolic N-defects around Ni sites can be transformed to a stable pyridinic N dominant Ni-N₂ coordination structure with promoted kinetics toward the CO₂-to-CO conversion. Both the CO selectivity and productivity increase markedly after the reconstruction, reaching a high CO Faradaic efficiency of 96% at mild overpotential of 590 mV and a large CO current density of 33 mA cm^-2 at 890 mV. X-ray adsorption spectroscopy and density functional theory (DFT) calculations reveal this defective local N environment decreases the restraint on central Ni atoms and provides enough space to facilitate the adsorption and activation of CO₂ molecule, leading to a reduced energy barrier for CO₂ reduction.     

Ultra‐High Surface Area Nitrogen‐Doped Carbon Aerogels Derived From a Schiff‐Base Porous Organic Polymer Aerogel for CO2 Storage and Supercapacitors

Nitrogen‐doped carbon aerogels (NCAs) have received great attention for a wide range of applications, from thermal electronics to waste water purification, heavy metal or gas adsorption, energy storage, and catalyst supports. Herein NCAs are developed via the synthesis of a Schiff‐base porous organic polymer aerogel followed by pyrolysis. By controlling the pyrolysis temperature, the polymer aerogel can be simply converted into porous NCAs with a low bulk density (5 mg cm^?3), high surface area (2356 m² g^?1), and high bulk porosity (70%). The NCAs containing 1.8–5.3 wt% N atoms exhibit remarkable CO₂ uptake capacities (6.1 mmol g^?1 at 273 K and 1 bar, 33.1 mmol g^?1 at 323 K and 30 bar) and high ideal adsorption solution theory selectivity (47.8) at ambient pressure. Supercapacitors fabricated with NCAs display high specific capacitance (300 F g^?1 at 0.5 A g^?1), fast rate (charge to 221 F g^?1 within only 17 s), and high stability (retained >98% capacity after 5000 cycles). Asymmetric supercapacitors assembled with NCAs also show high energy density and power density with maximal values of 30.5 Wh kg^?1 and 7088 W kg^?1, respectively. The outstanding CO₂ uptake and energy storage abilities are attributed to the ultra‐high surface area, N‐doping, conductivity, and rigidity of NCA frameworks.     

Accelerating CO2 Electroreduction to CO Over Pd Single‐Atom Catalyst

The electrochemical conversion of carbon dioxide (CO₂) into value‐added chemicals is regarded as one of the promising routes to mitigate CO₂ emission. A nitrogen‐doped carbon‐supported palladium (Pd) single‐atom catalyst that can catalyze CO₂ into CO with far higher mass activity than its Pd nanoparticle counterpart, for example, 373.0 and 28.5 mA mg^?1_Pd, respectively, at ?0.8 V versus reversible hydrogen electrode, is reported. A combination of in situ X‐ray characterization and density functional theory (DFT) calculation reveals that the Pd? N₄ site is the most likely active center for CO production without the formation of palladium hydride (PdH), which is essential for typical Pd nanoparticle catalysts. Furthermore, the well‐dispersed Pd? N₄ single‐atom site facilitates the stabilization of the adsorbed CO₂ intermediate, thereby enhancing electrocatalytic CO₂ reduction capability at low overpotentials. This work provides important insights into the structure‐activity relationship for single‐atom based electrocatalysts.     

Atomic Ni Anchored Covalent Triazine Framework as High Efficient Electrocatalyst for Carbon Dioxide Conversion

Electrochemically driven carbon dioxide (CO₂) conversion is an emerging research field due to the global warming and energy crisis. Carbon monoxide (CO) is one key product during electroreduction of CO₂; however, this reduction process suffers from tardy kinetics due to low local concentration of CO₂ on a catalyst's surface and low density of active sites. Herein, presented is a combination of experimental and theoretical validation of a Ni porphyrin‐based covalent triazine framework (NiPor‐CTF) with atomically dispersed NiN₄ centers as an efficient electrocatalyst for CO₂ reduction reaction (CO₂RR). The high density and atomically distributed NiN₄ centers are confirmed by aberration‐corrected high‐angle annular dark field scanning transmission electron microscopy and extended X‐ray absorption fine structure. As a result, NiPor‐CTF exhibits high selectivity toward CO₂RR with a Faradaic efficiency of >90% over the range from ?0.6 to ?0.9 V for CO conversion and achieves a maximum Faradaic efficiency of 97% at ?0.9 V with a high current density of 52.9 mA cm^?2, as well as good long‐term stability. Further calculation by the density functional theory method reveals that the kinetic energy barriers decreasing for *CO₂ transition to *COOH on NiN₄ active sites boosts the performance.     

A Zn–CO2 Flow Battery Generating Electricity and Methane

Metal–CO₂ batteries represent an economical and efficient CO₂ utilization technique, which provides a mechanism combining CO₂ reduction with electricity generation instead of electricity input. Existing metal–CO₂ batteries generally work in a closed system by recycling CO₂. In this study, a flow battery is designed with a hollow fiber of carbon nanotubes (cathode), Zn wire (anode), and 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (electrolyte). The battery can continuously consume CO₂ to produce CH₄ under ambient conditions and promptly output the gaseous product through the hollow fiber, with a Faradaic efficiency up to 94%. Simultaneously, the battery generates electricity, with an energy density of 288.3 Wh kg^?1 (based on the zinc mass) and a stability up to 8 days. The high selectivity and efficiency of the battery is attributed to a water‐shuttling assisted proton mechanism and delicate electrode–electrolyte interplay. Moreover, the Zn anode is electrochemically renewed and the battery assembled with the regenerated Zn anode restores battery performances to the former level. The renewable characteristic implies that, if the regeneration of Zn anode is coupled to excessive renewable energy sources, then the Zn–CO₂ flow battery will be promising to accomplish a net reduction of CO₂ emission.     

Understanding Boosted Selective CO2-to-CO Photoreduction with Pure Water Vapor over Hierarchical Biomass-Derived Carbon Matrix

Solar-driven CO₂ reduction reaction (CO₂RR) with water into carbon-neutral fuels is of great significance but remains challenging due to thermodynamic stability and kinetic inertness of CO₂. Biomass-derived nitrogen-doped carbon (N-C_b) have been considered as promising earth-abundant photocatalysts for CO₂RR, although their activities are not ideal and the reaction mechanism is still unclear. Herein, an efficient catalyst is developed for CO₂-to-CO conversion realized on diverse N-C_b materials with hierarchical pore structures. It is demonstrated that the CO₂-to-CO conversion preferentially takes place on positively charged carbon atoms next to pyridinic-N using two representatives treated pollens with the largest difference in pyridinic-N density and N content as model photocatalysts. Systematic experimental results indicate that surface local electric field originating from charge separation can be boosted by hierarchical pore structures, doped N, as well as pyridinic-N. Mechanistic studies reveal that positively charged carbon atoms next to pyridinic-N serve as active sites for CO₂RR, reduce the energy barrier on the formation of CO*, and facilitate the CO₂RR performance. All these benefits cooperatively contribute to treated chrysanthemum pollen catalyst exhibiting excellent CO formation rate of 203.2 µmol h⁻¹ g⁻¹ with 97.2% selectivity in pure water vapor. These results provide a new perspective into CO₂RR on N-C_b, which shall guide the design of nature-based photocatalysts for high-performance solar-fuel generation.     

Pre-Activation of CO2 at Cobalt Phthalocyanine-Mg(OH)2 Interface for Enhanced Turnover Rate

Cobalt phthalocyanine (CoPc) anchored on heterogeneous scaffold has drawn great attention as promising electrocatalyst for carbon dioxide reduction reaction (CO₂RR), but the molecule/substrate interaction is still pending for clarification and optimization to maximize the reaction kinetics. Herein, a CO₂RR catalyst is fabricated by affixing CoPc onto the Mg(OH)₂ substrate primed with conductive carbon, demonstrating an ultra-low overpotential of 0.31 ± 0.03 V at 100 mA cm⁻² and high faradaic efficiency of >95% at a wide current density range for CO production, as well as a heavy-duty operation at 100 mA cm⁻² for more than 50 h in a membrane electrode assembly. Mechanistic investigations employing in situ Raman and attenuated total reflection surface-enhanced infrared absorption spectroscopy unravel that Mg(OH)₂ plays a pivotal role to enhance the CO₂RR kinetics by facilitating the first-step electron transfer to form anionic *CO₂⁻ intermediates. DFT calculations further elucidate that introducing Lewis acid sites help to polarize CO₂ molecules absorbed at the metal centers of CoPc and consequently lower the activation barrier. This work signifies the tailoring of catalyst-support interface at molecular level for enhancing the turnover rate of CO₂RR.     

A New Strategy for Accelerating Dynamic Proton Transfer of Electrochemical CO2 Reduction at High Current Densities

Developing single-atom electrocatalysts with high activity and superior selectivity at a wide potential window for CO₂ reduction reaction (CO₂RR) still remains a great challenge. Herein, a porous Ni N C catalyst containing atomically dispersed Ni N₄ sites and nanostructured zirconium oxide (ZrO₂@Ni-NC) synthesized via a post-synthetic coordination coupling carbonization strategy is reported. The as-prepared ZrO₂@Ni-NC exhibits an initial potential of −0.3 V, maximum CO Faradaic efficiency (F.E.) of 98.6% ± 1.3, and a low Tafel slope of 71.7 mV dec⁻¹ in electrochemical CO₂RR. In particular, a wide potential window from −0.7 to −1.4 V with CO F.E. of above 90% on ZrO₂@Ni-NC far exceeds those of recently developed state-of-the-art CO₂RR electrocatalysts based on Ni N moieties anchored carbon. In a flow cell, ZrO₂@Ni-NC delivers a current density of 200 mA cm⁻² with a superior CO selectivity of 96.8% at −1.58 V in a practical scale. A series of designed experiments and structural analyses identify that the isolated Ni N₄ species act as real active sites to drive the CO₂RR reaction and that the nanostructured ZrO₂ largely accelerates the protonation process of *CO₂⁻ to *COOH intermediate, thus significantly reducing the energy barrier of this rate-determining step and boosting whole catalytic performance.     

Micro-Electrode with Fast Mass Transport for Enhancing Selectivity of Carbonaceous Products in Electrochemical CO2 Reduction

During electrochemical carbon dioxide (CO₂) reduction on copper electrodes in an aqueous electrolyte, one of the key challenges is the competition between hydrogen evolution and CO₂ reduction, especially under large current density. Here, micro-electrodes are designed with a copper wire as the substrate, which shows improved mass transport compared to the planar electrode. The Faradaic efficiency for C₂₊ products reaches 79% with a partial geometric current density − 77.7 mA cm⁻² on Cu₂O nanowire/micro-electrode, which is 3.7 times higher than Cu₂O nanowire/planar-electrode. The authors also designed CuO and metallic Cu with micro-electrode as substrate and observed enhanced selectivity for carbonaceous products, proving the universality of the concept. The improved activity is attributed to the fast mass transport of CO₂ to the catalytic interface and thus the suppression of hydrogen production.     

Targeted Synergy between Adjacent Co Atoms on Graphene Oxide as an Efficient New Electrocatalyst for Li–CO2 Batteries

Li–CO₂ batteries are an attractive technology for converting CO₂ into energy. However, the decomposition of insulating Li₂CO₃ on the cathode during discharge is a barrier to practical application. Here, it is demonstrated that a high loading of single Co atoms (≈5.3%) anchored on graphene oxide (adjacent Co/GO) acts as an efficient and durable electrocatalyst for Li–CO₂ batteries. This targeted dispersion of atomic Co provides catalytically adjacent active sites to decompose Li₂CO₃. The adjacent Co/GO exhibits a highly significant sustained discharge capacity of 17 358 mA h g^?1 at 100 mA g^?1 for >100 cycles. Density functional theory simulations confirm that the adjacent Co electrocatalyst possesses the best performance toward the decomposition of Li₂CO₃ and maintains metallic‐like nature after the adsorption of Li₂CO₃.