Cu2O Catalyst Research Articles

Stabilization of Cu2O catalyst via strong electronic interaction for selective electrocatalytic CO2 reduction to ethanol

While cuprous oxide (Cu2O) remains the most efficient and viable electrocatalyst for the electrochemical conversion of CO2 to ethanol, its reduction to Cu during the catalytic CO2RR process poses a barrier to its industrial application. To address this challenge, we have reported a highly stable Cu2O-based catalyst by introducing pseudo-capacitive NiCo2O4 intermediate layers. The current densities observed on the surface of the prepared NF@NiCo2O4@Cu2O remained consistent over a 15-hour stability test, demonstrating excellent durability that exceeds that of the NF@Cu2O electrode by more than 200 %. Experimental characterization and DFT analysis indicate that the exceptional stability is primarily attributed to the pseudo-capacitive NiCo2O4 interlayer with cyclic charge–discharge properties, where NiCo2O4 can capture and eliminate accumulated reduced electrons around Cu2O under strong electronic interactions and release electrons through catalytic reduction to produce hydrogen. Furthermore, the NiCo2O4@Cu2O (111) heterostructure significantly reduces the Gibbs free energy (ΔG) required for C-C coupling of *CO intermediates compared to Cu2O (111). This mechanism establishes a cyclic charge–discharge process in order to prevent reduction of Cu2O into copper monomers. As a result, NF@NiCo2O4@Cu2O demonstrates a C2H5OH faradaic efficiency of 56.9 % at −0.5 V vs. RHE, surpassing many other Cu-based catalytic electrodes. This work provides new insights into studying strong electronic interaction structures to eliminate electron enrichment at the catalytic site for stabilizing catalysts and also offers an effective strategy for designing catalysts that maintain long-term stability in industrial applications.

Efficient CO2 reduction to C2 products in a Ce-TiO2 photoanode-driven photoelectrocatalysis system using a Bnanometer Cu2O cathode

Excessive emission of CO2 into the atmosphere has caused significant environmental issues. Photoelectrocatalytic (PEC) reduction of CO2 is an effective method that combines the benefits of both photo- and electrocatalysis. This process effectively minimizes CO2 emissions, enhances the efficiency of CO2 reduction, and diminishes energy consumption during the reduction process. In this work, we have successfully developed a photoelectrochemical (PEC) system, integrating a Ce-doped TiO2 film as the photoanode and Cu2O as the dark cathode, in which the 4 % Ce-TiO2 film photoanode demonstrated the best performance. Electrochemical performance data revealed that the Cu2O catalysts, characterized by their octahedral geometry that optimally presents active sites for CO2 reduction, displayed superior activity in converting CO2. Through a straightforward hydrothermal synthesis, we crafted three-dimensional, flower-like TiO2 thin films. The strategic incorporation of cerium into the TiO2 matrix not only enhanced the material's crystallinity but also resulted in a uniform and compact morphology. This modification significantly narrowed the band gap of TiO2, thereby boosting its photocatalytic capabilities. In the system where a 4 % Ce-TiO2 thin film photoanode was used to drive the PEC reduction of CO2, the octahedral Cu2O catalyst demonstrated the highest selectivity for C2 products. This occurred at a reaction voltage of −1.4 V vs. RHE, resulting in a total Faraday efficiency of 67.33 %. Notably, this Faraday efficiency is double the one produced from the electrocatalytic (EC) system. This work demonstrates that the use of a 4 % Ce-TiO2 film as a photoanode is able to solve the photocorrosion problem of the Cu2O catalyst while employing a photovoltaic combination to enhance the selectivity to C2 products.

Enhanced CO2 photoreduction in pure water systems by surface-reconstructed asymmetric Mn–Cu sites

Metal-organic frameworks (MOFs) with abundant pores are excellent adsorbents for metal ions. However, the subsequent treatment of used MOFs and their reutilization still lack promising solutions. Herein, the surface-restructured Mn-doped Cu2O (RM-Cu2O) catalyst containing asymmetric Mn−Cu sites is prepared by glucose reduction using the spent Cu-based MOF (HKUST-1) as the precursor. The RM-Cu2O catalyst shows good potential in tunable photocatalytic syngas (CO and H2) production in a pure water system. The syngas ratios can be tuned from ∼1:2 to ∼1:1 by increasing CO production. DFT calculations and photoelectrochemical tests confirm that the asymmetric Mn−Cu sites on the RM-Cu2O catalyst accelerate the photogenerated charge transport and optimize CO2 adsorption and activation. In situ irradiation X-ray photoelectron spectroscopy is conducted to investigate the dynamic charge transport and reactions on the RM-Cu2O catalyst. Based on in situ Fourier transform infrared spectroscopy and simulations, the mechanism of photocatalytic syngas production is elucidated. This work provides a promising solution for the resource utilization of the spent MOFs-based adsorbents and photocatalytic energy development.

Synergistic degradation of p-nitrophenol using peroxymonosulfate activated with a bimetallic Mn3O4–Cu2O catalyst: Investigation of strong interactions between metal oxides

The use of efficient, eco-friendly catalysts is essential for activating peroxymonosulfate (PMS) to degrade organic contaminants in aqueous media. In this study, we developed a novel approach to fabricating bimetallic MnCu catalysts (Mn:Cu molar ratios: 10:1, 5:1, 3:1, and 2:1) comprising tetragonal Mn3O4 and cubic Cu2O. MnCu-5:1 exhibited superior catalytic activity for the degradation of p-nitrophenol (PNP) using PMS because of the synergistic interplay between Mn and Cu. Experimental and density functional theory (DFT) calculation data revealed that the mixed valence states and strong interactions between Mn and Cu in the MnCu-5:1 system increased the electron transfer efficiency and promoted electron transfer to PMS. The results of quenching experiments elucidated a primary radical mechanism and minor nonradical pathway for the PNP degradation over the MnCu-5:1/PMS system. DFT calculations confirmed a relatively high adsorption energy of the Mn3O4–Cu2O (MnCu) composite, indicating enhanced catalytic performance. The superior reactivity of the composite was verified by analyzing its density of states and electrostatic difference potential. Our findings offer fresh perspectives for harnessing the synergistic potential of less toxic mixed metal oxides for controlling catalytic properties and help achieve a better understanding of the activation mechanism for contaminant degradation over MnCu catalysts.

The fabrication of potassium ion modification on Cu2O(111) for enhanced propylene oxide selectivity: Insights from density functional theory

Utilizing the alkali metal effect to enhance catalyst performance is an effective approach in the development of highly efficient catalysts. Herein, we report a K+ ion-modification strategy on Cu-based catalysts for the direct epoxidation of propylene (DEP) using molecular oxygen, a reaction deemed as one of the “dream reactions” in heterogeneous catalysis. By elaborately engineering of K+-modified Cu2O(111) catalyst, we unveil the versatile roles played by K+ ions in promoting catalytic performance for DEP. Firstly, K+ ions stabilize the surface coordination structures of Cu2O(111). Secondly, K+ ions make the dissociation of adsorbed O2* less likely, thus facilitating the reaction of propylene with O2*. Furthermore, both K+ and two-coordinated Cu+ serve as active centers in this reaction. Lastly, K+ ions create unique surface coordination structures favorable for propylene oxide (PO) formation. The density functional theory (DFT) calculations demonstrate that the effective utilization of the alkali metal effect can engineer highly efficient Cu-based catalysts for DEP.

Insights into the Origin of Activity Enhancement via Tuning Electronic Structure of Cu2O towards Electrocatalytic Ammonia Synthesis.

The insight of the activity phase and reaction mechanism is vital for developing high-performance ammonia synthesis electrocatalysts. In this study, the origin of the electronic-dependent activity for the model Cu2O catalyst toward ammonia electrosynthesis with nitrate was probed. The modulation of the electronic state and oxygen vacancy content of Cu2O was realized by doping with halogen elements (Cl, Br, I). The electrocatalytic experiments showed that the activity of the ammonia production depends strongly on the electronic states in Cu2O. With increased electronic state defects in Cu2O, the ammonia synthesis performance increased first and then decreased. The Cu2O/Br with electronic defects in the middle showed the highest ammonia yield of 11.4 g h-1 g-1 at -1.0 V (vs. RHE), indicating that the pattern of change in optimal ammonia activity is consistent with the phenomenon of volcano curves in reaction chemistry. This work highlights a promising route for designing NO3-RR to NH3 catalysts.

XPS valence band observable light-responsive system for photocatalytic acid Red114 dye decomposition using a ZnO–Cu2O heterojunction

ZnO–Cu2O composites were made as photocatalysts in a range of different amounts using an easy, cheap, and environment-friendly coprecipitation method due to their superior visible light activity to remove pollutants from the surrounding atmosphere. X-ray diffraction and Fourier transform infrared spectroscopy (FT-IR) have demonstrated that ZnO–Cu2O catalysts are made of highly pure hexagonal ZnO and cubic Cu2O. X-ray photoelectron spectroscopy has confirmed that there is a substantial interaction between the two phases of the resultant catalyst. The optical characterizations of the synthesized ZnO–Cu2O composite were done via UV–vis reflectance spectroscopy. Due to the doping on ZnO, the absorption range of the ZnO–Cu2O catalyst is shifted from the ultraviolet to the visible region due to diffuse reflection. The degradation efficiency is affected by the Ratio of ZnO: Cu2O and ZnO–Cu2O composite with a proportion of 90:10 exhibited the most prominent photocatalytic activity on Acid Red 114, with a pseudo-first-order rate constant of 0.05032 min−1 that was 6 and 11 times greater than those of ZnO and Cu2O, respectively. The maximum degradation efficiency is 97 %. The enhanced photocatalytic activity of the composite is caused by the synergistic interaction of ZnO and Cu2O, which improves visible light absorption by lowering band gap energy and decreasing the rate at which the electron-hole pairs recombine. The scavenging experiment confirmed that hydroxyl radical was the dominant species for the photodegradation of Acid Red 114. Notably, the recycling test demonstrated the ZnO–Cu2O photocatalyst was highly stable and recyclable. These results suggest that the ZnO–Cu2O mix might be able to clean up environmental pollutants when it meets visible light.

Atomically Dispersed Ga Synergy Lewis Acid‐Base Pairs in F‐doped Mesoporous Cu2O for Efficient Eletroreduction of CO2 to C2+ Products

AbstractElectroreduction of CO2 into high‐value chemicals and fuels driven is an effective way to alleviate the environmental crisis, but it suffers from poor activity and low selectivity of the catalyst. Single‐atom catalysts have excellent selectivity and the highest atomic efficiency, and are widely used in the 2‐electron transfer to produce CO. However, electroreduction of CO2 to C2+ products involves complex processes such as multi‐electron reaction and competitive adsorption, so single‐atom catalysis is often powerless. Herein, a single‐atom Ga‐anchored F‐doped Cu2O catalyst with dual active sites is reported. The Lewis acid‐base pairs and Ga single atom sites promote the adsorption/activation of CO2 and the dissociation of water molecules, respectively, enhance the coverage of *CO and *H, and their synergy optimizes the reaction path. At a high current density of 600 mA cm−2, the FEC2+ reached 72.8 ± 3.2% with remarkable stability. Experiments and theory calculations demonstrate that the dual sites increase the coverage of *CO and *H, and the key intermediate *CO is transformed into *CHO through protonation reaction, which changes the reaction path from the C─C coupling (*OCCO) to the protonation followed by C─C coupling (*OCCHO) with low energy barrier, greatly improving the selectivity for C2+ products.

Boosting the electroreduction of CO2 to liquid products via nanostructure engineering of Cu2O catalysts

The electrochemical reduction of CO2 presents a promising pathway for storing intermittent renewable energy in the form of chemical bonds, thereby mitigating CO2 emissions and enabling the production of sustainable fuels. In this work, we demonstrate nanoscale engineering of oxygen vacancy and morphology simultaneously on Cu2O catalysts for electrochemical reduction of CO2 to liquid products (formate and ethanol). By comparing the performance of cube- and tetrakaidecahedron-like Cu2O catalysts, we have demonstrated that the flower-like Cu2O catalyst, enclosed with rich oxygen vacancy defects, exhibited superior performance in the reduction of CO2 to liquid products. Moreover, the synergetic role of Cu+ also contributed to the enhanced activity by promoting CO2 adsorption and facilitating C–C coupling. As a result, the peak Faradaic efficiency (FE) for liquid products of 95.5 % was obtained, associated with a high ethanol FE of 52.6 % and formation rate of 23.8 μmol h−1 cm−2 within a H-cell. Furthermore, within a flow cell configuration, we have observed a significant improvement in the generation of formate, maintaining FE values above 70 % even under high current densities of up to 400 mA cm−2. In-situ Raman spectroscopic measurements allow us to identify and track key intermediates involved in the CO2 reduction to formate and ethanol. This detailed understanding of the reaction pathways adds to our fundamental knowledge and provides valuable insights for the development of morphology-controlled electrocatalysts targeting efficient conversion of CO2 into liquid products.

N-doped Cu2O with the tunable Cu0 and Cu+ sites for selective CO2 electrochemical reduction to ethylene

The electrochemical carbon dioxide reduction reaction (CO2RR) to high value-added fuels or chemicals driven by the renewable energy is promising to alleviate global warming. However, the selective CO2 reduction to C2 products remains challenge. Cu-based catalyst with the specific Cu0 and Cu+ sites is important to generate C2 products. This work used nitrogen (N) to tune amounts of Cu0 and Cu+ sites in Cu2O catalysts and improve C2-product conversion. The controllable Cu0/Cu+ ratio of Cu2O catalyst from 0.16 to 15.19 was achieved by adjusting the N doping amount using NH3/Ar plasma treatment. The major theme of this work was clarifying a volcano curve of the ethylene Faraday efficiency as a function of the Cu0/Cu+ ratio. The optimal Cu0/Cu+ ratio was determined as 0.43 for selective electroreduction CO2 to ethylene. X-ray spectroscopy and density functional theory (DFT) calculations were employed to elucidate that the strong interaction between N and Cu increased the binding energy of NCu bond and stabilize Cu+, resulting in a 92.3% reduction in the potential energy change for *CO-*CO dimerization. This study is inspiring in designing high performance electrocatalysts for CO2 conversion.

Enhancing local K+ adsorption by high-density cube corners for efficient electroreduction of CO2 to C2+ products.

Reducing carbon dioxide (CO2) to high value-added chemicals using renewable electricity is a promising approach to reducing CO2 levels in the air and mitigating the greenhouse effect, which depends on high-efficiency electrocatalysts. Copper-based catalysts can be used for electroreduction of CO2 to produce C2+ products with high added value, but suffer from poor stability and low selectivity. Herein, we propose a strategy to enhance the field effect by varying the cubic corner density on the surface of Cu2O microspheres for improving the electrocatalytic performance of CO2 reduction to C2+ products. Finite element method (FEM) simulation results show that the high density of cubic corners helps to enhance the local electric field, which increases the K+ concentration on the catalyst surface. The results of CO2 electroreduction tests show that the FEC2+ of the Cu2O catalyst with high-density cubic corners is 71% at a partial current density of 497 mA cm-2. Density functional theory (DFT) calculations reveal that Cu2O (111) and Cu2O (110) can effectively reduce the energy barrier of C-C coupling and improve the FEC2+ at high K+ concentrations relative to Cu2O (100). This study provides a new perspective for the design and development of efficient CO2RR catalysts.

Granular protruded irregular Cu2O catalysts for efficient CO2 reduction to C2 products

The electrochemical reduction of carbon dioxide (CO2) to high-energy multi-carbon compounds is a significant challenge. Efforts have been made to design efficient catalysts for high selectivity toward multi-carbon products. In this study, granular protruded irregular Cuprous oxide (Cu2O) nanoparticles were synthesized using a simple water bath wet chemical reduction method. Polyethylene glycol (PEG) was utilized as a directing agent to control the morphology of Cu2O in the process. The optimized irregular Cu2O (ir-Cu2O) catalyst exhibits a remarkable faraday efficiency of 69.3% (±3.3%) for double-carbon compounds (C2), which is significantly higher than that of polyhedral Cu2O (p-Cu2O) (50.4%±1.1%) synthesized without adding PEG. Cu2O nanoparticles with irregular shape featuring randomly distributed spherical protrusions offer more active sites for CO2 adsorption than p-Cu2O catalysts, which is beneficial for the conversion of CO2 to C2. In addition, in situ infrared spectra reveal that ir-Cu2O reduces CO2 to C2 mainly through the coupling of the CO* and CHO*, thereby promoting the formation of C2. These findings provide valuable insights for the design of high-efficiency electrocatalysts for CO2 electroreduction to C2.

Ag decorated-Cu2O catalysts with enhanced selectivity for CO2 electroreduction toward C2+ products

Copper-based electrocatalysts have been widely used to generate C2+ products via the electrocatalytic carbon dioxide reduction reaction (CO2RR) because the catalysts possess unique properties for C-C coupling. Tandem catalysis is an attractive concept for C2+ production, enhancing selectivity and activity by combining CO-generating catalysts with Cu-based catalysts. Herein, the ability of Ag decoration to improve the selectivity of the Cu2O catalysts for C2+ production was investigated. The Ag/Cu2O catalyst with 10 wt% Ag content on the Cu2O surface (10 Ag/Cu2O) exhibited high Faradaic efficiency (FE) of 48% for C2+ products at –0.99 V (vs. RHE). Moreover, the partial current density of C2+ products on the 10 Ag/Cu2O was improved by 33% compared to the bare Cu2O catalyst. The intermediate (CO) generated on the Ag surface migrates by diffusion and/or sequential desorption-re-adsorption from Ag to Cu at the Ag-Cu interface of the Ag/Cu2O, increasing CO coverage on the Cu surface. The increase in CO coverage on the Cu surface of the Ag/Cu2O catalysts after decoration with Ag effectively reduces the hydrogen evolution reaction (HER), enhancing C-C coupling to generate C2+ products on the Ag/Cu2O. In addition, density functional theory (DFT) calculation results also revealed that Ag provides more CO2 activation sites, increasing CO coverage and reducing hydrogen adsorption energy, thus suppressing HER and improving the selectivity of CO2RR toward C2+ production.

Identifying the facet-dependent active sites of Cu2O for selective C-N coupling toward electrocatalytic urea synthesis

Understanding the activity phases and reaction mechanisms at the atomic level is essential for the design of electrocatalysts. Herein we investigate the origin of the facet-dependent activity of model Cu2O catalyst for C-N coupling toward electrocatalytic urea synthesis. It was found that the activity of urea synthesis depends on the crystalline facets of Cu2O. The Cu2O (100) facet exhibits higher urea activity and selectivity than the (110) facet, with an average urea yield of 62.4 mmol·g−1·h−1 at –1.5 V (RHE). By using Raman, UV–vis and XPS techniques, it was observed that Cu+ serves as active sites at (100) face of Cu2O, which promotes C-N coupling through synergistic interaction with Cu0. Furthermore, the combined results of operando ATR-SEIRAS and DFT calculations demonstrate that the Cu-Cu2O (100) facet facilitates electrocatalytic C-N coupling between *CO and *NH intermediates due to the reduced energy barriers of hydrogenated *NO on the Cu-Cu2O (100) facet.

Boosting C2+ production from photoelectrochemical CO2 reduction on gallium doped Cu2O

Photoelectrochemical CO2 reduction into C2+ products not only realizes the efficient conversion and utilization of CO2, but also provides a new way to synthesize value added hydrocarbons. However, it remains a grand challenge for highly selective synthesis of C2+ product due to the complexity of CO2 reduction and the coexistence of competitive reaction on the electrode surface. Herein we report a gallium doped Cu2O catalyst (Ga/Cu2O) prepared by a typical electrochemical deposition method via oriented growth on the surface of Cu mesh with easily controllable Ga contents. As the self-supporting electrode, it exhibits a highly efficient and selective CO2 reduction into C2+ products with Faradaic efficiencies of C2+, CH3CH2OH, and CH3CH2CH2OH as high as 20%, 6.5% and 6.64%, respectively at the potential of −1.8 V vs reversible hydrogen electrode (RHE). Experimental results show that Ga doping generated more oxygen vacancies via partial substitution in the lattice of Cu2O, resulting in rapid separation of the generated electron-hole pairs and regulating the electronic structure of catalyst surface and promotion of CO2 adsorption and activation. As a result, a higher *CO coverage and better C-C coupling probability on the surface of Ga/Cu2O were reached compared to those of unmodified Cu2O, which are responsible for the enhancement of the selectivity of CO2RR into C2+ products.

Nanograin-Boundary-Abundant Cu2O-Cu Nanocubes with High C2+ Selectivity and Good Stability during Electrochemical CO2 Reduction at a Current Density of 500 mA/cm2.

Surface and interface engineering, especially the creation of abundant Cu0/Cu+ interfaces and nanograin boundaries, is known to facilitate C2+ production during electrochemical CO2 reductions over copper-based catalysts. However, precisely controlling the favorable nanograin boundaries with surface structures (e.g., Cu(100) facets and Cu[n(100)×(110)] step sites) and simultaneously stabilizing Cu0/Cu+ interfaces is challenging, since Cu+ species are highly susceptible to be reduced into bulk metallic Cu at high current densities. Thus, an in-depth understanding of the structure evolution of the Cu-based catalysts under realistic CO2RR conditions is imperative, including the formation and stabilization of nanograin boundaries and Cu0/Cu+ interfaces. Herein we demonstrate that the well-controlled thermal reduction of Cu2O nanocubes under a CO atmosphere yields a remarkably stable Cu2O-Cu nanocube hybrid catalyst (Cu2O(CO)) possessing a high density of Cu0/Cu+ interfaces, abundant nanograin boundaries with Cu(100) facets, and Cu[n(100)×(110)] step sites. The Cu2O(CO) electrocatalyst delivered a high C2+ Faradaic efficiency of 77.4% (56.6% for ethylene) during the CO2RR under an industrial current density of 500 mA/cm2. Spectroscopic characterizations and morphological evolution studies, together with in situ time-resolved attenuated total reflection-surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) studies, established that the morphology and Cu0/Cu+ interfacial sites in the as-prepared Cu2O(CO) catalyst were preserved under high polarization and high current densities due to the nanograin-boundary-abundant structure. Furthermore, the abundant Cu0/Cu+ interfacial sites on the Cu2O(CO) catalyst acted to increase the *CO adsorption density, thereby increasing the opportunity for C-C coupling reactions, leading to a high C2+ selectivity.

Boosting ultralong chemiluminescence for the self-powered time-resolved immunosensor

The construction of an immunosensor based on ultralong chemiluminescence is challenged due to the shortage of highly efficient initiator for long and stable catalysis. Herein, the heterogeneous Au/Pt@CuO/Cu2O catalyst was used to investigate the structure-activity relationship, while Au/Pt significantly promotes the activity of CuO/Cu2O to catalyze H2O2 and thus produces ·OH and O2•- radicals in highly alkaline solutions, resulting in the strong and long chemiluminescence in the reaction with luminol (10 mL, more than 4 min with 1 μg catalyst). By using the Au/Pt@CuO/Cu2O as the label in the immunoassay, the strong and long chemiluminescence could initiate the photocurrent of the photoelectrochemical (PEC) substrate, and the luminescence time could influence the photocurrent extinction time, thus a self-powered time-resolved PEC immunosensor was developed to detect furosemide, showing a linear relationship between the extinction time and the logarithm of concentrations from 10−3 to 1 μg/L. This work not only experimentally verifies that the Pt–O–Cu bond in heterogeneous catalysts breaks the pH limitation of the Fenton reaction, but also realizes the chemiluminescence for self-powered time-resolved immunosensor, thereby expanding the portable applicability of chemiluminescence in food safety inspection, health monitoring, and biomedical detection without external light source.

Zhang-Rice singlets state formed by two-step oxidation for triggering water oxidation under operando conditions

The production of ecologically compatible fuels by electrochemical water splitting is highly desirable for modern industry. The Zhang-Rice singlet is well known for the superconductivity of high-temperature superconductors cuprate, but is rarely known for an electrochemical catalyst. Herein, we observe two steps of surface reconstruction from initial catalytic inactive Cu1+ in hydrogen treated Cu2O to Cu2+ state and further to catalytic active Zhang-Rice singlet state during the oxygen evolution reaction for water splitting. The hydrogen treated Cu2O catalyst exhibits a superior catalytic activity and stability for water splitting and is an efficient rival of other 3d-transition-metal catalysts. Multiple operando spectroscopies indicate that Zhang-Rice singlet is real active species, since it appears only under oxygen evolution reaction condition. This work provides an insight in developing an electrochemical catalyst from catalytically inactive materials and improves understanding of the mechanism of a Cu-based catalyst for water oxidation.

Electroreduction of CO 2 to C 2 H 4 Regulated by Spacing Effect: Mechanistic Insights from DFT Studies

It is crucial to construct an efficient catalyst with high activity and excellent selectivity for realizing CO 2 electroreduction reaction (CO 2 ER) to high-value-added chemicals, especially the C2 products. Density functional theory (DFT) provides a powerful tool for investigating the promotional effect on C2 selectivity of finely tuned catalyst structures, which is currently difficult to control using experimental techniques, such as interatomic distances. In the work, 5 Cu 2 O catalyst models are constructed with different Cu-Cu atomic spacing ( d Cu - Cu ). The results of DFT calculations show that adjusting the d Cu - Cu can effectively tailor the electronic structures of active sites, enhance catalytic activity, and improve product selectivity. Specifically, the Cu atom pair spaced at d Cu - Cu = 2.5 Å could optimize the adsorption configuration of *CO and enhance the binding strength of *CO, thus improving *CO adsorption energy and reducing the energy barrier of C-C coupling. The work proves the feasibility of spacing effect in enhancing the C 2 H 4 selectivity of CO 2 ER and provides a new idea for the catalyst modification for other reactions of polyprotons-coupled electrons.

Nanocavity-enriched Porous Cu2O Catalyst for Selective CO2 Reduction to Multicarbon Products through the Nanoconfinement Effect

Nanocavity-enriched Porous Cu2O Catalyst for Selective CO2 Reduction to Multicarbon Products through the Nanoconfinement Effect