Electrocatalytic CO2 Reduction Reaction Research Articles

Mo4+-Doped CuS Nanosheet-Assembled Hollow Spheres for CO2 Electroreduction to Ethanol in a Flow Cell.

Electrocatalytic CO2 reduction reaction (CO2RR) to ethanol has been widely researched for potential commercial application. However, it still faces limited selectivity at a large current density. Herein, Mo4+-doped CuS nanosheet-assembled hollow spheres are constructed to address this issue. Mo4+ ion doping modifies the local electronic environments and diversifies the binding sites of CuS, which increases the coverage of linear *COL and produces bridge *COB for subsequent *COL-*COH coupling toward ethanol production. The optimal Mo9.0%-CuS can electrocatalyze CO2 to ethanol with a faradaic efficiency of 67.5% and a partial current density of 186.5 mA cm-2 at -0.6 V in a flow cell. This work clarifies that doping high valence transition metal ions into Cu-based sulfides can regulate the coverage and configuration of related intermediates for ethanol production during the CO2RR in a flow cell.

Tuning the Microenvironment of Co−N4 Ensemble for Co Single‐Atom Catalysts for Electrocatalytic CO2 Reduction

AbstractSingle‐atom catalysts (SACs), with their well‐defined structure, serve as an efficient catalyst model for studying the structure‐performance relation in the electrocatalytic CO2 reduction reaction (CO2RR). Current CO2RR research primarily focus on the coordination interactions between metal single atoms and coordinated ligands, while the impact of the metal SAC′s microenvironment remains largely unexplored. Herein, we generate three microenvironments for a CoN4 ensemble by using different nitrogen sources to prepare Co SACs, i. e. pyridine‐type Co−N4 (Co−N4 SACPhen), the pyrrole‐type Co−N4 (Co−N4 SACDp) and the mixed‐type Co−N4(Co−N4 SACMm). It reveals that the Co−N4 SACPhen contributes to CO generation with 99.5 % selectivity at −0.76 vs RHE, whereas the Co−N4 SACDp accelerates a severe hydrogen evolution reaction. Experimental studies confirmed that the Co−N4 SACPhen possesses distinctive electrochemical properties and electronic structure, with the pyridine‐N being more conducive to electron accumulation and exhibited a higher electron delocalization, thereby promoting the generation of CO. This study deepens our understanding of the cobalt SAC′s microenvironment‘s influence on CO2RR.

High-Entropy La(FeCuMnMgTi)O3 Nanoparticles as Heterogeneous Catalyst for CO2 Electroreduction Reaction.

In this work, La(FeCuMnMgTi)O3 HEO nanoparticles with a perovskite-type structure are synthesized and used in the electrocatalytic CO2 reduction reaction (CO2RR). The catalyst demonstrates high performance as an electrocatalyst for the CO2RR, with a Faradaic efficiency (FE) of 92.5% at a current density of 21.9 mA cm-2 under -0.75 V vs a saturated calomel electrode (SCE). Particularly, an FE above 54% is obtained for methyl isopropyl ketone (C5H10O, MIPK) at a partial current density of 16 mA cm-2, overcoming all previous works. Besides, the as-prepared HEO catalyst displays robust stability in the CO2RR. The excellent catalytic performance of La(FeCuMnMgTi)O3 is ascribed to the synergistic effect between the electronic effects associated with five cations occupying the high-entropy sublattice sites and the oxygen vacancies within the perovskite structure of the HEO. Finally, DFT calculations indicate that Cu plays a vital role in the catalytic activity of the La(FeCuMnMgTi)O3 HEO nanoparticles toward C2+ products.

Reaction Environment Regulation for Electrocatalytic CO2 Reduction in Acids

AbstractThe electrocatalytic CO2 reduction reaction (CO2RR) is a sustainable route for converting CO2 into value‐added fuels and feedstocks, advancing a carbon‐neutral economy. The electrolyte critically influences CO2 utilization, reaction rate and product selectivity. While typically conducted in neutral/alkaline aqueous electrolytes, the CO2RR faces challenges due to (bi)carbonate formation and its crossover to the anolyte, reducing efficiency and stability. Acidic media offer promise by suppressing these processes, but the low Faradaic efficiency, especially for multicarbon (C2+) products, and poor electrocatalyst stability persist. The effective regulation of the reaction environment at the cathode is essential to favor the CO2RR over the competitive hydrogen evolution reaction (HER) and improve long‐term stability. This review examines progress in the acidic CO2RR, focusing on reaction environment regulation strategies such as electrocatalyst design, electrode modification and electrolyte engineering to promote the CO2RR. Insights into the reaction mechanisms via in situ/operando techniques and theoretical calculations are discussed, along with critical challenges and future directions in acidic CO2RR technology, offering guidance for developing practical systems for the carbon‐neutral community.

Regulating Cu Oxidation State for Electrocatalytic CO2 Conversion into CO with Near-Unity Selectivity via Oxygen Spillover.

Cu-based catalysts are the most intensively studied in the field of electrocatalytic CO2 reduction reaction (CO2RR), demonstrating the capacity to yield diverse C1 and C2+ products albeit with unsatisfactory selectivity. Manipulation of the oxidation state of Cu sites during CO2RR process proves advantageous in modulating the selectivity of productions, but poses a formidable challenge. Here, an oxygen spillover strategy is proposed to enhance the oxidation state of Cu during CO2RR by incorporating the oxygen donor Sb2O4. The Cu-Sb bimetallic oxide catalyst attains a remarkable CO2-to-CO selectivity approaching unity, in stark contrast to the diverse product distribution observed with bare CuO. The exceptional Faradaic efficiency of CO can be maintained across a wide range of potential windows of ≈700mV in 1m KOH, and remains independent of the Cu/Sb ratio (ranging from 0.1:1 to 10:1). Correlative calculations and experimental results reveal that oxygen spillover from Sb2O4 to Cu sites maintains the relatively high valence state of Cu during CO2RR, which diminishes the binding strength of *CO, thereby achieving heightened selectivity in CO production. These findings propose the role of oxygen spillover in CO2RR over Cu-based catalysts, and shed light on the rational design of highly selective CO2 reduction catalysts.

Investigating the influence of oxygen doping in modulating product distribution for electrocatalytic CO2 reduction reaction

Efficient carbon recycling hinges on a comprehensive understanding of the mechanics behind electrocatalytic carbon dioxide reduction reactions (ECO2RR). Here, we have engineered, in-situ growth of CuO featured on O-doped gCN (COG) and ex-situ growth of CuO on bare gCN (CG) respectively, functioned as platforms fordisengaging the fundamental of ECO2RR. The COG holds substantial capacity compared to CG for efficient conversion of CO2 into hydrocarbons and initiated the C2 product pathway with enlarged faradaic efficiency (FE). The experimental results indicate that the COG enhanced the product conversion of CH3OH (FE = 61.5% ± 0.5), C2H5OH (FE = 24.7% ± 0.5), and HCOO– (FE = 6.1% ± 0.5) at −1.1 V Vs RHE. Meanwhile, the CG exhibited the maximum conversion of CO2 into CH3OH (FE = 56.4% ± 0.5) at the same potential range. For the CG, the partial current density of CH3OH (JCH3OH) is −1.8 mA cm−2, whereas COG exhibited −4.9 mA cm−2. Interestingly, in this ECO2RR, the study of oxygen doping demonstrated that feasible CO2 conversion, due to its affinity towards CO2 and high donor density.

Construction of low-symmetrical charge-neutral Sn12-oxo football cage with the functionalized ligand

Tin-oxo clusters, as molecular model compounds of tin oxide materials, have attracted increasing attention. Although various tin-oxo clusters have been obtained, the systemic studies on ligand functionalization of tin-oxo clusters remain to be well developed. In this study, we adopted 3-aminopyrazine-2-carboxylic acid (HAPZC) as the functionalized ligand, and successfully synthesized a novel tin-oxo cluster [(n-BuSn)12(OH)6O14 (APZC)2]·2H2O (CTGU-SnC-3). Due to the functionalization of the APZC ligands, the structure and charge of Sn12 cage in CTGU-SnC-3 are all different from those of reported cationic football cage. This Sn12 cage in CTGU-SnC-3 presents the interesting low-symmetrical football framework with the functionalized ligands. Different from the reported cationic football cages, the CTGU-SnC-3 is charge-neutral structure without any counteranions. Moreover, the CTGU-SnC-3 exhibits hydrophobic behavior and catalytic activity in electrocatalytic CO2 reduction reaction.

Transition-Metal Porphyrin-Based MOFs In Situ-Derived Hybrid Catalysts for Electrocatalytic CO2 Reduction.

Excellent electrocatalytic CO2 reduction reaction activity has been demonstrated by transition metals and nitrogen-codoped carbon (M-N-C) catalysts, especially for transition-metal porphyrin (MTPP)-based catalysts. In this work, we propose to use one-step low-temperature pyrolysis of the isostructural MTPP-based metal-organic frameworks (MOFs) and electrochemical in situ reduction strategies to obtain a series of hybrid catalysts of Co nanoparticles (Co NPs) and MTPP, named Co NPs/MTPP (M = Fe, Co, and Ni). The in situ introduction of Co NPs can efficiently enhance the electrocatalytic ability of MTPP (M = Fe, Co, and Ni) to convert CO2 to CO, particularly for FeTPP. Co NPs/FeTPP endowed a high CO faradaic efficiency (FECOmax = 95.5%) in the H cell, and the FECO > 90.0% is in the broad potential range of -0.72 to -1.22 VRHE. In addition, the Co NPs/FeTPP achieved 145.4 mA cm-2 at a lower potential of -0.70 VRHE with an FECO of 94.7%, and the CO partial currents increased quickly to reach 202.2 mA cm-2 at -0.80 VRHE with an FECO of 91.6% in the flow cell. It is confirmed that Co NPs are necessary for hybrid catalysts to get superior electrocatalytic activity; Co NPs also can accelerate H2O dissociation and boost the proton supply capacity to hasten the proton-coupled electron-transfer process, effectively adjusting the adsorption strength of the reaction intermediates.

Transition metal (Fe, Co, Ni)-doped cuprous oxide nanowire arrays as self-supporting catalysts for electrocatalytic CO2 reduction reaction to ethylene

The transition metal (Fe, Co, Ni)-doped cuprous oxide (Cu2O) nanowire arrays on Cu mesh (CM) (M-Cu2O@CM, M = Fe, Co, Ni) are successfully synthesized for the electrocatalytic CO2 reduction reaction (CO2RR) to ethylene (C2H4) through the simple calcination and impregnation-exchange methods. Systematic characterizations have demonstrated that the Ni/Co doping in Cu2O@CM is conducive to stabilizing the Cu+ sites due to the electron transfer from Cu2O to Ni/Co, while the Fe doping has the opposite effect. Consequently, they show the different electrocatalytic performances of Ni-Cu2O@CM > Co-Cu2O@CM > Cu2O@CM > Fe-Cu2O@CM for CO2RR to C2H4 in an H-cell. Among them, Ni-Cu2O@CM exhibits the ∼2.0-fold faradaic efficiency for C2H4 (58.2 % vs. 28.7 %) and the ∼2.5-fold current density (−37.6 vs. −15.0 mA·cm−2) at −1.1 V vs. RHE, as compared with Cu2O@CM. Further experiments reveal that during the electrocatalytic CO2RR, the Ni-Cu2O@CM can generate more *CO, which promotes the C–C coupling reaction. The activity of Co-Cu2O@CM is lower than Ni-Cu2O@CM because of the strong adsorption of *COOH, while the Fe-Cu2O@CM even exhibits a lower activity than Cu2O@CM. This work provides an insight into the effect of transition metal-doped Cu2O array on the electrocatalytic CO2RR to C2H4 products.

Impact of gas diffusion layer architecture on the performances of Cu-based electrodes for CO2 electroreduction to ethylene in flow reactors

Electrocatalytic CO2 reduction reaction (CO2RR) is a promising strategy to convert CO2 into fuels and building blocks for chemicals, exploiting renewable energy sources. Flow cells using gas diffusion electrodes (GDEs) instead of simple H-cells are required to achieve higher production rates. In a GDE, CO2 diffuses through a porous gas diffusion layer (GDL) and reaches the active sites located in the catalyst layer; the GDL is a crucial component that can affect the performance of the GDE. In this work, we aimed to establish the parameters of the GDL that influence the selectivity toward the different CO2 reduction products in an alkaline flow reactor. We employed commercial Cu nanoparticles as electrocatalyst and selected a range of market-available GDLs: the structure, composition, and type of cracks of the GDL greatly influence the Faradaic Efficiency (FE) of CO, H2, and ethylene (C2H4). With the emphasis on C2H4, it was found that using a crack-free GDE is essential to get higher FEC2H4. At the same time, larger and more abundant cracks are detrimental to C2H4 production and promote hydrogen evolution: for instance, the FEC2H4 varies in the wide range of 13–32%, from the highly cracked to the crack-free GDL. The presence of both sulfur and oxygen in the microporous layer (MPL) of the GDL helps shift the CO2RR selectivity toward CO. The (in)stability of the GDEs at high current density has been correlated with a change in the wetting properties of the GDE and a loss in hydrophobicity.

Reaction Environment Regulation for Electrocatalytic CO2 Reduction in Acids.

The electrocatalytic CO2 reduction reaction (CO2RR) is a sustainable route for converting CO2 into value-added fuels and feedstocks, advancing a carbon-neutral economy. The electrolyte critically influences CO2 utilization, reaction rate and product selectivity. While typically conducted in neutral/alkaline aqueous electrolytes, the CO2RR faces challenges due to (bi)carbonate formation and its crossover to the anolyte, reducing efficiency and stability. Acidic media offer promise by suppressing these processes, but the low Faradaic efficiency, especially for multicarbon (C2+) products, and poor electrocatalyst stability persist. The effective regulation of the reaction environment at the cathode is essential to favor the CO2RR over the competitive hydrogen evolution reaction (HER) and improve long-term stability. This review examines progress in the acidic CO2RR, focusing on reaction environment regulation strategies such as electrocatalyst design, electrode modification and electrolyte engineering to promote the CO2RR. Insights into the reaction mechanisms via in situ/operando techniques and theoretical calculations are discussed, along with critical challenges and future directions in acidic CO2RR technology, offering guidance for developing practical systems for the carbon-neutral community.

Hydrogen‐Bonded Organic Framework Supporting Atomic Bi−N2O2 Sites for High‐Efficiency Electrocatalytic CO2 Reduction

AbstractSingle atomic catalysts (SACs) offer a superior platform for studying the structure–activity relationships during electrocatalytic CO2 reduction reaction (CO2RR). Yet challenges still exist to obtain well‐defined and novel site configuration owing to the uncertainty of functional framework‐derived SACs through calcination. Herein, a novel Bi−N2O2 site supported on the (1 1 0) plane of hydrogen‐bonded organic framework (HOF) is reported directly for CO2RR. In flow cell, the target catalyst Bi1‐HOF maintains a faradaic efficiency (FE) HCOOH of over 90 % at a wide potential window of 1.4 V. The corresponding partial current density ranges from 113.3 to 747.0 mA cm−2. And, Bi1‐HOF exhibits a long‐term stability of over 30 h under a successive potential‐step test with a current density of 100–400 mA cm−2. Density function theory (DFT) calculations illustrate that the novel Bi−N2O2 site supported on the (1 1 0) plane of HOF effectively induces the oriented electron transfer from Bi center to CO2 molecule, reaching an enhanced CO2 activation and reduction. Besides, this study offers a versatile method to reach series of M−N2O2 sites with regulable metal centers via the same intercalation mechanism, broadening the platform for studying the structure–activity relationships during CO2RR.

Novel flexible aromatic Cu3 metal-organic π-cluster for electrocatalytic CO2 reduction reaction

Producing Cn products through electrocatalytic CO2 reduction reaction (CO2RR) is of great significance in addressing the global warming crisis. Organic-inorganic hybrid catalysts, characterized by precise and controllable active sites and metal-ligand synergistic interactions, can enhance the reaction activity and stability of Cu-based catalysts. Herein, based on density functional theory (DFT), a novel flexible aromatic Cu3 metal-organic π-cluster (Cu3-π cluster) was constructed, consisting of triple-atom active centers and pentalyne ligands. During the catalytic CO2RR process, the adsorption of H can promote the activation of CO2, this converts the competing hydrogen evolution reaction (HER) into promoting CO2RR. Enhanced aromaticity of its cluster core is credited with stabilizing the coadsorption of H and CO2 (H* + CO2*), consequently lowering the reaction free energy of the CO2 activation process. Research has shown that Cu3-π cluster have high catalytic activity for electrocatalytic CO2 generation of C2H4. Considering the solvation effect, the limit potential of this reaction is −0.60 V. Furthermore, the reaction free energies suggest that the Cu3-π cluster is more inclined to yield C2H4(g) products via COCO* coupling. Moreover, the high CO coverage at the triple-atom active centers not only makes it more challenging for this cluster to adsorb H, but also reduces the energy barrier of the COCO* coupling reaction.In the entire reaction pathway of C2H4(g), there exhibits dynamic self-adaptive behavior in the bond lengths and bond angles of the three Cu atoms in the cluster core, leading to fluctuations in aromaticity. The flexibility and aromaticity changes in this structure enable the Cu3-π cluster to better stabilize intermediates. This work provides theoretical guidance for the application of metal-organic π-clusters, accelerates the screening of catalysts for CO2RR, and provides powerful theoretical guidance for the structure-activity relationships between aromaticity and catalytic activity.

Elaborate Modulating Binding Strength of Intermediates via Three-component Covalent Organic Frameworks for CO2 Reduction Reaction.

The catalytic performance for electrocatalytic CO2 reduction reaction (CO2RR) depends on the binding strength of the reactants and intermediates. Covalent organic frameworks (COFs) have been adopted to catalyze CO2RR, and their binding abilities are tuned via constructing donor-acceptor (DA) systems. However, most DA COFs have single donor and acceptor units, which caused wide-range but lacking accuracy in modulating the binding strength of intermediates. More elaborate regulation of the interactions with intermediates are necessary and challenge to construct high-efficiency catalysts. Herein, the three-component COF with D-A-A units was first constructed by introducing electron-rich diarylamine unit, electron-deficient benzothiazole and Co-porphyrin units. Compared with two-component COFs, the designed COF exhibit elevated electronic conductivity, enhanced reducibility, high efficiency charge transfer, further improving the electrocatalytic CO2RR performance with the faradic efficiency of 97.2 % at -0.8 V and high activity with the partial current density of 27.85 mA cm-2 at -1.0 V which exceed other two-component COFs. Theoretical calculations demonstrate that catalytic sites in three-component COF have suitable binding ability of the intermediates, which are benefit for formation of *COOH and desorption of *CO. This work offers valuable insights for the advancement of multi-component COFs, enabling modulated charge transfer to improve the CO2RR activity.

Elaborate Modulating Binding Strength of Intermediates via Three‐component Covalent Organic Frameworks for CO2 Reduction Reaction

AbstractThe catalytic performance for electrocatalytic CO2 reduction reaction (CO2RR) depends on the binding strength of the reactants and intermediates. Covalent organic frameworks (COFs) have been adopted to catalyze CO2RR, and their binding abilities are tuned via constructing donor‐acceptor (DA) systems. However, most DA COFs have single donor and acceptor units, which caused wide‐range but lacking accuracy in modulating the binding strength of intermediates. More elaborate regulation of the interactions with intermediates are necessary and challenge to construct high‐efficiency catalysts. Herein, the three‐component COF with D‐A‐A units was first constructed by introducing electron‐rich diarylamine unit, electron‐deficient benzothiazole and Co‐porphyrin units. Compared with two‐component COFs, the designed COF exhibit elevated electronic conductivity, enhanced reducibility, high efficiency charge transfer, further improving the electrocatalytic CO2RR performance with the faradic efficiency of 97.2 % at −0.8 V and high activity with the partial current density of 27.85 mA cm−2 at −1.0 V which exceed other two‐component COFs. Theoretical calculations demonstrate that catalytic sites in three‐component COF have suitable binding ability of the intermediates, which are benefit for formation of *COOH and desorption of *CO. This work offers valuable insights for the advancement of multi‐component COFs, enabling modulated charge transfer to improve the CO2RR activity.

Asymmetric coordination engineering of active centers in MXene-based single atom catalysts for high-performance ECO2RR

Asymmetric coordination effect is an important concept in heterogeneous catalysis where both catalytic activity and product selectivity are serious influenced. However, this effect has rarely been understood because of the difficult in characterizing detailed coordination information. Here, by employing a theoretical study on electrocatalytic CO2 reduction reaction (ECO2RR) towards HCOOH over Ti3C2O2-based NS/NN co-coordinated transition metal single atom catalysts (TM-NS/NN-Ti3C2O2 SACs), we show that asymmetric coordination environments have great impact on the electronic structure of the active center. Both electron transferring ability and spin polarization of the active center are vital to optimize the adsorption and hydrogenation of key intermediates. As a result, both catalytic activity and product selectivity can be maximized. V-NN-Ti3C2O2 are predicted to promote high-throughput HCOOH generation process at operation applied potential of −0.32 with considerable electrochemical stability, surpassing most reported catalysts. This work demonstrates V-NN-Ti3C2O2 as high-performance ECO2RR catalysts, and highlights that the introduction of the concept of asymmetric coordination effect may offer a new insight into the rational design of more efficient SACs.

Theoretical Study of Electrocatalytic CO2 Reduction Mechanism on Typical MXenes under Realistic Conditions.

MXenes are a revolutionary class of two-dimensional materials that have been recently demonstrated to exhibit promising capability of electrocatalytic CO2 reduction reaction (CO2RR) in theory and experiment. In electrocatalytic reactions, the active phases, the mechanism, and the performance can be greatly influenced by electrochemical conditions such as applied electrode potential, pH, and electrolyte. Therefore, in this first-principles study, the stable surface structures of three typical MXenes (V2C, Mo2C, and Ti3C2) with variation of electrocatalytic conditions were determined by the Pourbaix phase diagrams. Additionally, the reaction mechanism for CO2RR toward C1 products was investigated based on the thermal dynamically stable phases. The computation revealed that surfaces of all three MXenes are dominated by H* termination throughout the practical CO2RR electrochemical condition ranges. Meanwhile, the bicarbonate ions, which serve as the major electrolyte in CO2RR, show thermal dynamic unfavorability to adsorb on the surfaces. Among the three types of MXenes, V2CH exhibits higher activity in generating CO and HCOOH through the CO2RR, while Mo2CH exhibits higher activity in producing HCHO, CH3OH, and CH4. This comprehensive study provides crucial insights into the mechanism of electrocatalytic CO2RR on MXenes under realistic electrochemical conditions.

Pd-Decorated Cu2O-Ag Catalyst Promoting CO2 Electroreduction to C2H4 by Optimizing CO Intermediate Adsorption and Hydrogenation.

Electrocatalytic CO2 reduction reaction (CO2RR) to high value-added products, such as ethylene (C2H4), offers a promising approach to achieve carbon neutrality. Although recent studies have reported that a tandem catalyst (for example, Cu-Ag systems) exhibits advantage in C2H4 production, its practical application is largely inhibited by the following: (1) a traditional tandem catalyst cannot effectively stabilize the *CO intermediate, resulting in sluggish C-C coupling, and (2) inadequate H2O activation ability hinders the hydrogenation of intermediates. To break through the above bottleneck, herein, palladium (Pd) was introduced into Cu2O-Ag, a typical conventional tandem catalyst, to construct a Cu2O-Pd-Ag ternary catalyst. Extensive experiment and density functional theory calculation prove that Pd can efficiently stabilize the *CO intermediate and promote the H2O activation, which contributes to the C-C coupling and intermediate hydrogenation, the key steps in the conversion of CO2 to C2H4. Beneficial to the efficient synergy of Cu2O, Pd, and Ag, the optimal Cu2O-Pd-Ag ternary catalyst achieves CO2RR toward C2H4 with a faradaic efficiency of 63.2% at -1.2 VRHE, which is higher than that achieved by Cu2O-Ag and most of other reported catalysts. This work is a fruitful exploration of a rare ternary catalyst, providing a new route for constructing an efficient CO2RR electrocatalyst.

Influence of Cu incorporation on activated carbon for CO2 adsorption and electrocatalytic hydrogen evolution reaction

Electrocatalytic hydrogen evolution reaction (HER) and CO2 reduction reaction (CO2RR) have emerged as promising approaches toward a sustainable and green society. In this study, potassium citrate-derived activated carbon (ACK) was synthesized and incorporated with copper (Cu) for electrocatalytic reduction under CO2 and N2 flows. The ACK sample exhibited high CO2 adsorption properties to generate different carbonate species and served as an electrocatalyst after Cu incorporation. To understand the competitive reactions of HER and CO2RR, different reaction conditions were applied. Under a CO2 flow, the Cu-ACK sample revealed a high and long-term current density of 0.9 V, and H2 (2.642 mmol) was determined as the major product, and CH3COOH, and C2H5OH as minor products. A reaction mechanism was proposed to elucidate the reaction path for the electrocatalytic CO2RR and HER.

Construction of Cobalt Porphyrin-Modified Cu2 O Nanowire Array as a Tandem Electrocatalyst for Enhanced CO2 Reduction to C2 Products.

Here, the molecule-modified Cu-based array is first constructed as the self-supporting tandem catalyst for electrocatalytic CO2 reduction reaction (CO2 RR) to C2 products. The modification of cuprous oxide nanowire array on copper mesh (Cu2 O@CM) with cobalt(II) tetraphenylporphyrin (CoTPP) molecules is achieved via a simple liquid phase method. The systematical characterizations confirm that the formation of axial coordinated Co-O-Cu bond between Cu2 O and CoTPP can significantly promote the dispersion of CoTPP molecules on Cu2 O and the electrical properties of CoTPP-Cu2 O@CM heterojunction array. Consequently, as compared to Cu2 O@CM array, the optimized CoTPP-Cu2 O@CM sample as electrocatalyst can realize the 2.08-fold C2 Faraday efficiency (73.2%vs 35.2%) and the 2.54-fold current density (-52.9vs -20.8mAcm-2 ) at -1.1V versus RHE in an H-cell. The comprehensive performance is superior to most of the reported Cu-based materials in the H-cell. Further study reveals that the CoTPP adsorption on Cu2 O can restrain the hydrogen evolution reaction, improve the coverage of * CO intermediate, and maintain the existence of Cu(I) at low potential.