Activity For CO2 Reduction Research Articles

Changing the Electron Acceptor Specificity of Rhodobacter capsulatus Formate Dehydrogenase from NAD+ to NADP.

Formate dehydrogenases catalyze the reversible oxidation of formate to carbon dioxide. These enzymes play an important role in CO2 reduction and serve as nicotinamide cofactor recycling enzymes. More recently, the CO2-reducing activity of formate dehydrogenases, especially metal-containing formate dehydrogenases, has been further explored for efficient atmospheric CO2 capture. Here, we investigate the nicotinamide binding site of formate dehydrogenase from Rhodobacter capsulatus for its specificity toward NAD+ vs. NADP+ reduction. Starting from the NAD+-specific wild-type RcFDH, key residues were exchanged to enable NADP+ binding on the basis of the NAD+-bound cryo-EM structure (PDB-ID: 6TG9). It has been observed that the lysine at position 157 (Lys157) in the β-subunit of the enzyme is essential for the binding of NAD+. RcFDH variants that had Glu259 exchanged for either a positively charged or uncharged amino acid had additional activity with NADP+. The FdsBL279R and FdsBK276A variants also showed activity with NADP+. Kinetic parameters for all the variants were determined and tested for activity in CO2 reduction. The variants were able to reduce CO2 using NADPH as an electron donor in a coupled assay with phosphite dehydrogenase (PTDH), which regenerates NADPH. This makes the enzyme suitable for applications where it can be coupled with other enzymes that use NADPH.

Inside Back Cover

The cover picture depicts the photocatalytic CO2 reduction by three cobalt‐based homogeneous molecular complexes with different coordination microenvironment. Under irradiation, [CoN3O]ClO4 shows better photocatalytic activity for CO2 reduction to CO, higher than that of [CoN4]ClO4, and [CoN3S]ClO4. Combining experimental and DFT calculations, it was possible to draw the conclusion that by modifying the direct coordination heteroatoms (O, N, S) of catalysts, the intermediate C—OH bond breakage was accelerated, improving the activity toward CO generation. More details are discussed in the article by Zhong et al. on page 3305—3310.image

Construction of oxygen-deficient In2O3/ZnIn2S4 with hollow tubular heterostructure for photocatalytic CO2 reduction to syngas and benzyl alcohol oxidation

To reduce the recombination of the photogenerated charge carriers (PCCs), increase the utilization of the PCCs may be an effective method. In this work, the heterojunction catalysts of MIL-68 derived In2O3 (IO) microtube and ZnIn2S4 (ZIS) nanosheets were prepared by self-template and in-situ growth strategy. By growing ZnIn2S4 nanosheets on the surface of oxygen-deficient IO microtube, these two distinct semiconductors are integrated into hierarchical tubular hybrids with heterogeneous interfacial contacts. To improve the utilization rate of PCCs, the photocatalytic CO2 reduction is proceeded on IO/ZIS composite coupling with benzyl alcohol (PhCH2OH) oxidation. With the mass ratio of IO and ZIS adjusted, 30% IO/ZIS performs the best photocatalytic activity of CO2 reduction, which is 64.19 times higher than that of pure ZIS. The largely enhanced photocatalytic activity of IO/ZIS is attributed to the intimate interfacial contacts between IO and ZIS, which accelerates the separation and migration of PCCs via the Z-scheme model. The separated electrons and holes are respectively participated in the CO2 reduction and the PhCH2OH oxidation, as the reduction and oxidation products are close to 1: 1. This work not only provides the guideline for the design and construction of complex semiconductor-based photocatalysts, but an effective way to increase the utilization of PCCs.

Bi/2 H-MoS2−x composite for efficient photo-thermal synergistic catalytic CO2 reduction

The high carrier recombination rate and poor photocorrosion resistance of intrinsic MoS2 lead to a poor photocatalytic CO2 reduction activity. Here, the photocatalytic CO2 reduction performance of 2 H-MoS2 was significantly enhanced by constructing Bi/2 H-MoS2−x composite and photo-thermal synergy strategy. Under the optimal conditions of 200 °C and 42 mW·cm-2 of 420 nm irradiation, Bi/2 H-MoS2−x exhibited an excellent photo-thermal synergistic catalytic activity of CO2 reduction with a CO production rate of 34.42 μmol-1·g-1·h-1. Mechanistic studies showed that the introduction of Bi greatly improved the light absorption ability, generated S vacancies as electron capture centers for rapid separation of photocarriers, and promoted the generation of key intermediates. The involvement of heat led to a photo-thermal synergistic effect, which accelerated the charge migration and surface reaction rate. Our work provides new insights into the development of efficient catalysts for CO2 reduction and the mechanism study of photo-thermal synergistic catalysis.

Designing of cobalt doped pyridine based covalent organic frameworks for efficient visible light driven CO2 reduction

Covalent organic frameworks (COF) are the class of compounds that impulses the boundaries of organic/polymer chemistry and materials science to achieve the exceptional control of predesigned long-range ordered structures. The present work deals with one-pot reaction of pyridine-2,6-diamine and terephthalaldehyde in pyrex tube at slightly elevated temperature and resulted in the formation of PDT/COF. The obtained PDT/COF was then functionalized using cobalt (Co@PDT/COF). The formation of COF and metal incorporation is confirmed by Fourier transform Infrared spectroscopy (FTIR). The simulated AB staggered stacking model for both PDT/COF and Co@PDT/COF correlate well with the observed PXRD pattern than AA eclipsed stacking. The theoretical findings using materials studio software showed increase in the porosity and interlayer spacing after the addition of Co to PDT/COF. The superior photocatalytic CO2 reduction activity is observed in Co@PDT/COF compared to PDT/COF. Co@PDT/COF was able to produce 13, 24 and 45 μmol g−1h−1 of H2, CH4 and CO, respectively. The obtained experimental optical properties were correlated well with Density functional theory (DFT) studies. Based on the characterization results, mechanism of photocatalysis has been discussed. Good stability and efficiency towards photocatalytic reduction CO2 in presence of the Co@PDT/COF shows its suitability for further research on pyridine based COFs for different applications.

Cd/Cd(OH)2 Nanosheets Enhancing the Electrocatalytic Activity of CO2 Reduction to CO.

Electric-driven conversion of carbon dioxide (CO2 ) to carbon monoxide (CO) under mild reaction conditions offers a promising approach to mitigate the greenhouse effect and the energy crisis. Surface engineering is believed to be one of the prospective methods for enhancing the electrocatalytic activity of CO2 reduction. Herein, hydroxyl (OH) groups were successfully introduced to cadmium nanosheets to form cadmium and cadmium hydroxide nanocomposites (i. e. Cd/Cd(OH)2 nanosheets) via a facile two-step method. The as-prepared Cd/Cd(OH)2 /CP (CP indicates carbon paper) electrode displays excellent electrocatalytic activity for CO2 reduction to produce CO. The Faradaic efficiency of CO reaches 98.3 % and the current density achieves 23.8 mA cm-2 at -2.0 V vs. Ag/Ag+ in a CO2 -saturated 30 wt% 1-butyl-3-methylimidazole hexafluorophosphate ([Bmim]PF6 )-65 wt% acetonitrile (CH3 CN)-5 wt% water (H2 O) electrolyte. And the CO partial current density can reach up to 71.6 mA cm-2 with the CO Faradaic efficiency of more than 85 % at -2.3 V vs. Ag/Ag+ , which stands out against Cd/CP, Cd(OH)2 /CP, and Cd/CdO/CP electrodes. The excellent electrocatalytic performance of the Cd/Cd(OH)2 /CP electrode can be attributed to its unique structural properties, suitable OH groups, perfect interaction with electrolyte, abundant active sites and fast electron transfer rate.

Fabrication of directly 2D Z-scheme CuTiO3/g-C3N4 with high photocatalytic activities for CO2 reduction and hydrogen production

Photocatalysts based on Z-scheme heterostructure have been extensively investigated for CO2 reduction and hydrogen production, which solve the problem of high electron-hole pair complexation and low reduction and oxidation capacity in photocatalysts. Here, two-dimensional CuTiO3/g-C3N4 (CTO/CN) photocatalysts with directly Z-scheme heterostructure are prepared by effective manipulation of different components of CuTiO3 (CTO) nanoparticles on 2D (two-dimension) porous g-C3N4 (CN) nanosheets via in-situ growing strategy. Benefited from the special electronic structure, it demonstrates that the 4.0 % CTO/CN sample has an excellent photocatalytic activity for the reduction of CO2 to H2 (at a speed of 19.56 μmol g−1 h−1) and CO (at a speed of 19.93 μmol g−1 h−1), which are upper than those of pure g-C3N4 by 43.5 and 17.1 times, respectively. Furthermore, the 4.0 % CTO/CN sample exhibits utstanding performance in electrocatalytic hydrogen production. This synthetic strategy is useful for constructing a 2D Z-scheme heterostructure for applications in energy-related areas.

Tuning N coordination environment in Ag[sbnd]N[sbnd]C single atom catalysts for efficient electrochemical CO2-to-Ethanol conversion

The rational modulation of the coordination environment of the active center of single-atom catalysts (SACs) is a potential strategy to improve the activity and selectivity of electrocatalytic CO2 reduction. We developed a series of single-atom Ag-anchored on N-doped carbon catalysts with different N-coordination environments by regulating the carbon source (glucose/graphene oxide, GO). Results demonstrated that the CO2-to-CO/C2H5OH pathway can be converted through reasonable regulation of the content of pyrrolic N and pyridine N. At a highly dominant pyrrolic N content of 40.0 %, the electrocatalyst of Ag-N-rGO0.025 M facilitates the formation of CO with a Faradaic efficiency (FE) of 69.7 %. By contrast, when the pyridine N content is 70.5 %, the best Ag-N-C0.05 M catalyst in the H-cell shows an FE of 42 % for C2H5OH at −0.97 V vs. RHE; moreover, the FE is stable at 40 % within 31 h. Density functional theory calculations further confirm that the pyrrolic N site is conducive to the conversion of CO2 to intermediate *CO, whereas pyridine N exhibits the highest binding energy (ΔG = -4.73 eV) to hold *CO intermediates for dimerization, consequently steering the pathway to the formation of C2H5OH. The results of this study provide novel insights into the rational design of carbon-based SACs based on efficient electrochemical CO2 reduction reaction and the regulation of CO2 selectivity and activity for C2H5OH production.

Well-designed glucose precursor carbon/g-C3N4 nanocomposite for enhanced visible light photocatalytic CO2 reduction activity

Fabrication of glucose precursor carbon-doped g-C3N4 nanocomposite (C/g-C3N4) for enhancing photocatalytic CO2 reduction into syngas (CO, CH4) has been investigated. The samples were successfully synthesized via a two-step thermal treatment and tested in a fixed bed reactor under visible light. The 0.2 % glucose precursor carbon-doped over g-C3N4 photocatalyst has demonstrated excellent activity in converting CO2 to CO and CH4 under visible light. The main product yield, CO of 898.9 μmol g-cat−1 was produced over 0.2 % C/g-C3N4, which is 4.6 folds the amount of CO obtained over the g-C3N4 (196.8 μmol g-cat−1). The XPS results confirmed the formation of a C-O-C bond between carbon and g-C3N4, resulting in a strong interaction between carbon and g-C3N4. Carbon-doped g-C3N4 possesses a narrow energy band and the ability to effectively absorb solar light, which enables efficient transportation of electrons generated by photon excitation. Possible reaction mechanisms for photoreduction of CO2 over carbon-doped g-C3N4 photocatalyst were proposed in order to understand the movement of electrons and holes. This work provides a simple method for designing highly efficient carbon-based photocatalysts for potential application in photocatalytic CO2 reduction using solar energy.

Synthesis, Structural Characterization and Photocatalytic CO2 Reduction Activity of a New Gd(III) Coordination Polymer with 6-Phenylpyridine-2-carboxylic acid and 4,4’-Bipyridine Ligands

A new Gd(III) coordination polymer, {[Gd(L1)3(H2O)2]∙L2}n (1) (HL1 = 6-phenylpyridine-2-carboxylic acid, L2 = 4,4’-bipyridine) was synthesized using 6-phenylpyridine-2-carboxylic acid, 4,4’-bipyridine, NaOH and GdCl3∙6H2O. The structure of Gd(III) coordination polymer has been characterized by IR and X-ray single crystal diffraction. The result of single crystal analysis indicates that fundamental unit of Gd(III) coordination polymer contains one Gd(III) ion, three L1 ligands, two coordinated water molecules and one uncoordinated 4,4’-bipyridine. In 1, the Gd(III) ion is eight-coordinated and surrounded by six O atoms from three L1 ligands and two O atoms from two coordinated water molecules, respectively. The complex 1 exhibits 1D chained structure by the bridging interactions of two carboxyl-oxygen atoms and O−H∙∙∙N hydrogen bonds interactions. The 1D chains are further connected by - stacking interactions to form 3D network architecture. The photocatalytic CO2 reduction activity of complex 1 has also been investigated. The complex 1 exhibits good CO2 reduction activity. With the increase of time, the yield of CO from 18.2 mmol/g in the first hour to 60.3 mmol/g in the third hour. And the CO selectivity has reached 100%. Copyright © 2023 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Active Site Engineering in Reticular Covalent Organic Frameworks for Photocatalytic CO2 Reduction

AbstractPhotochemical CO2 reduction using ubiquitous sunlight akin to natural photosynthesis is an effective approach for conversion of renewable energy into useful chemical feedstock. Driven by the need for earth‐abundant, inexpensive, and sustainable photocatalysts with practical applicability, covalent organic frameworks (COFs) have emerged as a new generation of molecularly defined semiconductors with tunable optoelectronic properties. These reticular frameworks with highly ordered, porous and crystalline structures can be tailor‐made by covalently combining organic building blocks to target specific functions. To date, numerous COFs have been reported, which show promising activity for photocatalytic CO2 reduction allowing to derive structure–property–function relationships. In this review, the different reported strategies are comprehensively analyzed and categorized for active site engineering in COF photocatalysts and the synthetic rationale and resulting catalytic activity for each approach are discussed. The recent advancements in terms of tailored photocatalyst design are then critically assessed, aspects of advanced materials characterization are analyzed, and future perspectives and challenges for the field are highlighted.

Insights into the Mechanism of CO2 Electroreduction by Molecular Palladium-Pyridinophane Complexes.

Herein, we report the synthesis, characterization, and electrocatalytic CO2 reduction activity of a series of Pd(II) complexes supported by tetradentate pyridinophane ligands. In particular, we focus on the electrocatalytic CO2 reduction activity of a Pd(II) complex supported by the mixed hard--soft donor ligand 2,11-dithia[3.3](2,6)pyridinophane (N2S2). We also provide spectroscopic evidence of a CO-induced decomposition pathway for the same catalyst, which provides insights into catalyst poisoning for molecular Pd CO2 reduction electrocatalysts.

Regulating interfacial coupling of 1D crystalline g-C3N4 nanorods with 2D Ti3C2Tx MXene for boosting photocatalytic CO2 reduction

Two-dimensional (2D) layered photocatalysts coupled with 2D Ti3C2Tx (T = OH, O, or F) MXene cocatalysts in 2D/2D configuration have been extensively studied for use in artificial photosynthesis. Unfortunately, the overall photoreaction efficiency of these cocatalysts is often limited by weak 2D/2D interfacial van der Waals interactions, high interfacial electrostatic barriers, and slow interfacial charge transfer. In this study, 1D crystalline g-C3N4 (CCN) nanorods are grown along the c-axis using the molten-salt method and assembled onto a 2D Ti3C2Tx substrate by freeze-drying-assisted interfacial coupling, forming a unique Schottky junction photocatalyst in a 1D/2D configuration with interfacial hydrogen bonds. Transfer of photoelectrons in the CCN nanorods could along the radial π-conjugated plane to the hydrogen-bonded 2D Ti3C2Tx in the 1D/2D configuration is more efficient than the slow interlayer charge transfer in catalysts with a conventional 2D/2D configuration. Consequently, the optimized 1D-CCN/2D-Ti3C2Tx hybrid photocatalyst assembled by freeze-drying (TC/CCN-FD) exhibited an outstanding photocatalytic CO2 reduction activity at a rate of 2.13 μmol g1 h1, being 5.6 and 8.9 times more efficient than the pristine 1D CCN and 2D bulk g-C3N4 counterparts, respectively. Moreover, the selectivity towards the multielectron reduction product (CH4) was significantly enhanced over TC/CCN-FD owing to the faster interfacial charge transfer across the CCN/Ti3C2Tx interface and the higher density of photoelectrons on the Ti3C2Tx cocatalysts. This work will inspire further studies on suppressing the interfacial charge transfer barrier by matching the interfacial crystal orientation and strengthening the interfacial interactions.

Porphyrin Supramolecular Nanoassembly/C3N4 Nanosheet S-Scheme Heterojunctions for Selective Photocatalytic CO2 Reduction toward CO.

The photocatalytic reduction of CO2 with H2O into valuable chemicals is a sustainable carbon-neutral technology for renewable energy; however, the photocatalytic activity and product selectivity remain challenging. Herein, an S-scheme heterojunction photocatalyst with superior CO2 photoreduction performance─porous C3N4 (CN) nanosheets anchored with zinc(II) tetra(4-cyanophenyl)porphyrin (ZnTP) nanoassemblies (denoted as ZnTP/CN)─was designed and prepared via a simple self-assembly process. The constructed ZnTP/CN heterojunction had rich accessible active sites, improved CO2 absorption capacity, and high charge carrier separation efficiency caused by the S-scheme heterojunction. As a result, the obtained ZnTP/CN catalyst exhibited considerable activity for photocatalytic CO2 reduction, yielding CO with a generation rate of 19.4 μmol g-1·h-1 and a high selectivity of 95.8%, which is much higher than that of pristine CN nanosheets (4.53 μmol g-1·h-1, 57.4%). In addition, theoretical calculations and in situ Fourier transform infrared spectra demonstrated that the Zn sites in the porphyrin unit favor CO2 activation and *COOH formation as well as CO desorption, thereby affording a high CO selectivity. This work provides insight into the design and fabrication of efficient S-scheme heterostructure photocatalysts for solar energy storage.

Hydrophilic calix[4]arene dye-sensitized Co/g-C3N4 composites with Co single atoms for enhanced visible-light-driven photocatalysis

Single-atom hybrid photocatalysts (Co/g-C3N4/C4EOP) composed of hydrophilic calixarene dyes (C4EOP) and graphite-phase carbon nitrite with monodispersed Co atoms (Co/g-C3N4) are prepared by a facile solution impregnation method, and their photocatalytic performances are evaluated in visible light-driven H2 evolution from water and CO2 conversion. The optimized Co/g-C3N4/C4EOP (1.0 wt%) catalyst exhibits moderate H2 production activity (511 μmol g−1 h−1) and good durability within 60 h (TONC4EOP value of 2255) under visible light. In contrast, the Co/g-C3N4/C4BTP (1.0 wt%) and Co/g-C3N4/M-EOP (1.0 wt%) show much lower activities than Co/g-C3N4/C4EOP (1.0 wt%) under the same conditions. This could be attributed to the higher molar extinction coefficient and better hydrophilicity of C4EOP compared to C4BTP with hydrophobic alkane groups and M-EOP with single D-π-A chain. In addition, Co/g-C3N4/C4EOP (1.0 wt%) catalyst displays highly selective photocatalytic activity for CO2 reduction to CO. This work provides a promising example for the development of efficient dye-sensitized photocatalytic system based on g-C3N4 with non-noble metal for the chemical utilization of solar energy.

S-Scheme ZIF-67/CuFe-LDH Heterojunction for High-Performance Photocatalytic H2 Evolution and CO2 to MeOH Production.

The S-scheme heterojunction photocatalyst holds potential for better photocatalysis owing to its capacity to broaden the light absorption range, ease electron-hole separation, extend the charge carrier lifespan, and maximize the redox ability. In this study, we integrate zeolitic imidazolate frameworks (ZIFs-67) with the CuFe-LDH composite, offering a straightforward approach towards creating a novel hybrid nanostructure, enabling remarkable performance in both photocatalytic hydrogen (H2) evolution and carbon dioxide (CO2) to methanol (MeOH) conversion. The ZIF-67/CuFe-LDH photocatalyst exhibits an enhanced photocatalytic hydrogen evolution rate of 7.4 mmol g-1 h-1 and an AQY of 4.8%. The superior activity of CO2 reduction to MeOH generation was 227 μmol g-1 h-1 and an AQY of 5.1%, and it still exhibited superior activity after continuously working for 4 runs with nearly negligible decay in activity. The combined spectroscopic analysis, electrochemical study, and computational data strongly demonstrate that this hybrid material integrates the advantageous properties of the individual ZIF-67 and CuFe-LDH exhibiting distinguished photon harvesting, suppression of the photoinduced electron-hole recombination kinetics, extended lifetime, and efficient charge transfer, subsequently boosting higher photocatalytic activities.

Modulating Bidirectional Catalytic Activity Through a RuNi Nanoalloy on Facile Candle Soot Carbon Towards Efficient Lithium‐CO2Mars Batteries

AbstractLithium‐CO2 batteries have been at the forefront of reducing CO2 emissions and addressing the present energy crisis. As the Martian atmosphere is 95 % CO2, this battery technology is ideal as a stand‐alone energy storage device on the planet. However, challenges such as low reversibility, high charging voltages, and poor cycling life restrict its practicability. The current study addresses these by increasing the reversibility of the active reaction sites on the cathode via a synergistic interaction between the RuNi nanoparticle catalyst and candle soot carbon (CSC). This helps the system achieve a full discharge capacity of 15207 mAh g−1 at a high current density of 200 mA g−1 with 99.3 % coulombic efficiency and an efficient cycling life of over 100 cycles at a higher current density of 500 mA g−1 for a limited capacity of 500 mAh g−1. Further, combining ex‐situ physical characterizations and density functional theory helps understand the underlying mechanism for improving the bidirectional CO2 reduction and evolution activities during discharging and charging. The study, thus using a bimetallic catalyst and carbon, provides an approach for a single solution towards addressing the dual challenges of regulating CO2 emissions on Earth and providing a constant energy source on Mars.

Strong Metal‐support Interactions in Photocatalysis: Fundamentals and Design Methods

AbstractEngineering the composition and geometry of metallic sites has become a popular manner to boost reaction rate and control reaction selectivity in heterogeneous catalysis. Many studies have been devoted to enhancing the stability of metallic nanoparticles during catalytic reactions by dispersion on metal oxide supports such as TiO2, CeO2 or Nb2O5. These supports not only modulate electronic properties and dispersion/stabilization of metallic nanoparticle but also influence catalytic selectivity, resulting in the so‐called “strong metal‐support interaction” (SMSI). In this minireview, we outlined the discovery and fundamentals of SMSI, as well as its extensive development over years. In addition, we summarized recent approaches developed to induce the construction of SMSI between different metal nanoparticles and metal oxide supports. Associated characterization microscopic and spectroscopic techniques were emphasized. Despite being a prevalent concept in catalysis, the number of studies on SMSI in heterogeneous photocatalysis has been even in limitation. Herein, we highlighted the beneficial effects of SMSI on boosting photocatalytic activity for CO2 reduction and H2 evolution reactions. In general, despite some controversial aspects of the SMSI, this concept offers wide opportunities ahead and encourages researchers to rethink the local active site localization and photocatalyst design.

Boosting the Proton-coupled Electron Transfer via Fe-P Atomic Pair for Enhanced Electrochemical CO2 Reduction.

Single-atom catalysts exhibit superior CO2 -to-CO catalytic activity, but poor kinetics of proton-coupled electron transfer (PCET) steps still limit the overall performance toward the industrial scale. Here, we constructed a Fe-P atom paired catalyst onto nitrogen doped graphitic layer (Fe1 /PNG) to accelerate PCET step. Fe1 /PNG delivers an industrial CO current of 1 A with FECO over 90 % at 2.5 V in a membrane-electrode assembly, overperforming the CO current of Fe1 /NG by more than 300 %. We also decrypted the synergistic effects of the P atom in the Fe-P atom pair using operando techniques and density functional theory, revealing that the P atom provides additional adsorption sites for accelerating water dissociation, boosting the hydrogenation of CO2 , and enhancing the activity of CO2 reduction. This atom-pair catalytic strategy can modulate multiple reactants and intermediates to break through the inherent limitations of single-atom catalysts.

Boosting the Proton‐coupled Electron Transfer via Fe−P Atomic Pair for Enhanced Electrochemical CO2 Reduction

AbstractSingle‐atom catalysts exhibit superior CO2‐to‐CO catalytic activity, but poor kinetics of proton‐coupled electron transfer (PCET) steps still limit the overall performance toward the industrial scale. Here, we constructed a Fe−P atom paired catalyst onto nitrogen doped graphitic layer (Fe1/PNG) to accelerate PCET step. Fe1/PNG delivers an industrial CO current of 1 A with FECO over 90 % at 2.5 V in a membrane‐electrode assembly, overperforming the CO current of Fe1/NG by more than 300 %. We also decrypted the synergistic effects of the P atom in the Fe−P atom pair using operando techniques and density functional theory, revealing that the P atom provides additional adsorption sites for accelerating water dissociation, boosting the hydrogenation of CO2, and enhancing the activity of CO2 reduction. This atom‐pair catalytic strategy can modulate multiple reactants and intermediates to break through the inherent limitations of single‐atom catalysts.