Cu4 Cluster Research Articles

A cluster-nanozyme-coenzyme system mimicking natural photosynthesis for CO2 reduction under intermittent light irradiation

Natural photosynthesis utilizes solar energy to convert water and atmospheric CO2 into carbohydrates through all-weather light/dark reactions based on molecule-based enzymes and coenzymes, inspiring extensive development of artificial photosynthesis. However, development of efficient artificial photosynthetic systems free of noble metals, as well as rational integration of functional units into a single system at the molecular level, remain challenging. Here we report an artificial system, the assembly system of Cu6 cluster and cobalt terpyridine complex, that mimics natural photosynthesis through precise integration of nanozyme complexes and ubiquinone (coenzyme Q) on Cu6 clusters. This biomimetic system efficiently reduces CO2 to CO in light reaction, achieving a production rate of 740.7 μmol·g−1·h−1 with high durability for at least 188 hours. Notably, our system realizes the decoupling of light and dark reactions, utilizing the phenol-evolutive coenzyme Q acting as an electron reservoir. By regulating the stabilizer of coenzyme Q, the dark reaction time can be extended up to 8.5 hours, which fully meets the natural day/night cycle requirements. Our findings advance the molecular design of artificial systems that replicate the comprehensive functions of natural photosynthesis.

Electronic and photocatalytic properties of Cu4 cluster-modified Ag/g-C3N4 single-atom catalysts: A hybrid DFT study

Increasing the active sites on the catalyst surface has been a key goal to increase the catalyst efficiency. This paper presents an efficient conversion of solar energy into chemical energy, realized by a Cu4 cluster-assisted single-atom catalyst (Ag-doped g-C3N4). The catalyst enhances charge transfer and light absorption, and the unique advantages of this approach in the field of photocatalysis are substantiated by density functional theory. Under the synergistic effect of Cu4 clusters, the electronic state density distribution of the Ag single-atom catalyst substrate is drastically altered, which realizes the increase of substrate active sites and rapid charge separation and transfer. Compared with the pristine substrate g-C3N4, the new electronic state distribution and the generation of impurity energy levels lead to the narrowing of the band gap from 2.77 to 1.83 eV, accelerating the transfer and separation of electrons and holes, and enlarging the visible light absorption range from 410 to 760 nm, thus improving the solar energy utilization. Despite the reduced band gap, the conduction and valance band edges of (Ag, Cu4) codoped g-C3N4 still have sufficient potential to split water. Therefore, to improve the photocatalytic performance under visible light, simultaneous codoping of the Ag single atom and Cu4 cluster on g-C3N4 is an effective strategy. The study provides theoretical support for further optimization of single-atom catalysts.

Tailoring Electrocatalytic Hydrogen Evolution Activity in Topological Triangular Metal–Organic Frameworks

AbstractMetal–organic frameworks (MOFs) have attracted considerable attention in catalysis due to their exceptional structural and chemical tunability. However, high electrical conductivity is rare in MOFs, hindering their practical applications toward catalytic reactions. Recently, 2D topological MOFs stand out for the unique topologically nontrivial electronic structures. Particularly, their high electrical conductivity and chemical tunability make them promising candidates as high‐performance catalysts. In this study, theoretical investigations are conducted into the intrinsic electronic properties and chemical activity of a 2D topological Cu‐1,3,5‐tris(pyridyl)benzene (Cu‐TPyB) framework. It is found that the coordination environment of Cu with pyridyl groups plays a crucial role in modulating the electron density around the Fermi level, thereby enhancing the catalytic activity of Cu‐TPyB toward electrochemical hydrogen evolution reaction (HER). Furthermore, substituting the single embedded Cu atom with Cu3 and Cu4Bi3 clusters further increases the electron density around the Fermi level. Specifically, the Cu4Bi3‐TPyB framework exhibits superior HER activity, which is attributed to its high electron density contributed by the p orbitals of Bi and the d orbitals of Cu. This work introduces a novel approach for optimizing the catalytic activity of 2D MOFs and developing high‐performance catalysts.

Milling-Induced "Turn-off" Luminescence in Copper Nanoclusters.

Atomically precise copper nanoclusters (NCs) attract research interest due to their intense photoluminescence, which enables their applications in photonics, optoelectronics, and sensing. Exploring these properties requires carefully designed clusters with atomic precision and a detailed understanding of their atom-specific luminescence properties. Here, we report two copper NCs, [Cu4(MNA)2(DPPE)2] and [Cu6(MNA-H)6], shortly Cu4 and Cu6, protected by 2-mercaptonicotinic acid (MNA-H2) and 1,2-bis(diphenylphosphino)ethane (DPPE), showing "turn-off" mechanoresponsive luminescence. Single-crystal X-ray diffraction reveals that in the Cu4 cluster, two Cu2 units are appended with two thiols, forming a flattened boat-shaped Cu4S2 kernel, while in the Cu6 cluster, two Cu3 units form an adamantane-like Cu6S6 kernel. High-resolution electrospray ionization mass spectrometry studies reveal the molecular nature of these clusters. Lifetime decay profiles of the two clusters show the average lifetimes of 0.84 and 1.64 μs, respectively. These thermally stable Cu NCs become nonluminescent upon mechanical milling but regain their emission upon exposure to solvent vapors. Spectroscopic data of the clusters match well with their computed electronic structures. This work expands the collection of thermally stable and mechanoresponsive luminescent coinage metal NCs, enriching the diversity and applications of such materials.

Supported Cu3 cluster on N-doped graphene: An efficient triatom catalyst for CO electroreduction to propanol at low potential

Electroreduction of carbon monoxide into high-energy fuel is an excellent energy strategy for sustainable development, but the high yield of multi-carbon products remains a difficult challenge. Inspired by the successful synthesis of various trimer metal clusters and studies on electrocatalysis of CO to C3 products by Cu-based catalysts, Cu3 supported on N-doped graphene structures (Cu3@NG) are investigated as electrocatalysts for CORR toward propanol in this paper. Due to the appropriate Cu-Cu bond length, the moderate charge of the Cu site, mild CO adsorption energy, and 100 % CO coverage, the absorbed 3*CO substance can form the critical *CO-CO-CO intermediate with a rather low kinetic barrier of 0.25 eV. The limiting potential of the whole process for the formation of propanol is just −0.15 V. Our work not only showed that Cu3@NG is an excellent catalyst for the formation of propanol with high selectivity at low potential but also indicated that the *CO coverage can greatly reduce the CO hydrogenation potential and bonding of some intermediates such as *CH2O. This research will provide a new idea for the material design of products tending to multi-carbon.

In situ Construction of Single‐Atom Electronic Bridge on COF to Enhance Photocatalytic H2 Production

AbstractPhotocatalytic hydrogen production is one of the most valuable technologies in the future energy system. Here, we designed a metal‐covalent organic frameworks (MCOFs) with both small‐sized metal clusters and nitrogen‐rich ligands, named COF‐Cu3TG. Based on our design, small‐sized metal clusters were selected to increase the density of active sites and shorten the distance of electron transport to active sites. While another building block containing nitrogen‐rich organic ligands acted as a node that could in situ anchor metal atoms during photocatalysis and form interlayer single‐atom electron bridges (SAEB) to accelerate electron transport. Together, they promoted photocatalytic performance. This represented the further utilization of Ru atoms and was an additional application of the photosensitizer. N2‐Ru‐N2 electron bridge (Ru‐SAEB) was created in situ between the layers, resulting in a considerable enhancement in the hydrogen production rate of the photocatalyst to 10.47 mmol g−1 h−1. Through theoretical calculation and EXAFS, the existence position and action mechanism of Ru‐SAEB were reasonably inferred, further confirming the rationality of the Ru‐SAEB configuration. A sufficiently proximity between the small‐sized Cu3 cluster and the Ru‐SAEB was found to expedite electron transfer. This work demonstrated the synergistic impact of small molecular clusters with Ru‐SAEB for efficient photocatalytic hydrogen production.

Electrocatalytic micro-environment regulation of ZIF-67 with broadened pore structure and unsaturated coordination sites for oxygen evolution reaction

The atomically precise mental nanoclusters have been widely explored in catalysis. However, the easy aggregation of clusters limits their application. The porous structure of metal-organic framework can prevent the aggregation and growth of clusters. In this work, a copper-phosphine complex: Cu2(dppm)2(PF6)2 (Cu2) was synthesized by one-pot method and then reacted with hydrogen sulfide to obtain a tetranuclear copper cluster: Cu4(S)(dppm)4(PF6)2 (Cu4). The two copper clusters were successfully introduced into Zeolitic imidazole frameworks-67 (ZIF-67) to form Cu2-ZIF-67 and Cu4-ZIF-67. It found that after the introduction of Cu cluster, the pore size of ZIF-67 was increased leading to more exposed Co2+ and more unsaturated coordination mental sites, which is beneficial for electrochemical oxygen evolution reaction (OER). The OER ability of pure ZIF-67 was enhanced after the introduction of Cu2 and Cu4 clusters, in which Cu4-ZIF-67 displayed the best electrochemical performance. At 10 mA cm−2, it requires an overpotential of 340 mV. The lower Tafel slope and smaller charge transfer resistance reflect its faster dynamic process. This work provides a new idea for the development of OER electrocatalysts.

In situ Construction of Single-Atom Electronic Bridge on COF to Enhance Photocatalytic H2 Production.

Photocatalytic hydrogen production is one of the most valuable technologies in the future energy system. Here, we designed a metal-covalent organic frameworks (MCOFs) with both small-sized metal clusters and nitrogen-rich ligands, named COF-Cu3TG. Based on our design, small-sized metal clusters were selected to increase the density of active sites and shorten the distance of electron transport to active sites. While another building block containing nitrogen-rich organic ligands acted as a node that could in situ anchor metal atoms during photocatalysis and form interlayer single-atom electron bridges (SAEB) to accelerate electron transport. Together, they promoted photocatalytic performance. This represented the further utilization of Ru atoms and was an additional application of the photosensitizer. N2-Ru-N2 electron bridge (Ru-SAEB) was created in situ between the layers, resulting in a considerable enhancement in the hydrogen production rate of the photocatalyst to 10.47 mmol g-1 h-1. Through theoretical calculation and EXAFS, the existence position and action mechanism of Ru-SAEB were reasonably inferred, further confirming the rationality of the Ru-SAEB configuration. A sufficiently proximity between the small-sized Cu3 cluster and the Ru-SAEB was found to expedite electron transfer. This work demonstrated the synergistic impact of small molecular clusters with Ru-SAEB for efficient photocatalytic hydrogen production.

Nature of CuxCe1-xO2 solid solution catalysts

Identifying the local environments of active sites of CuxCe1-xO2 solid solution for low-temperature CO oxidation remains significant challenges. In this study, we coupled density functional theory and microkinetic modeling to thoroughly investigate local structures of CuxCe1-xO2 solid solution catalysts, as well as its catalytic performance for low-temperature CO oxidation. Combined with the infrared spectra simulations, we propose that the substitution of Cu3 or Cu4 clusters for one Ce atom accounts for the experimentally observed vibrational peaks of the adsorbed CO, rather than the Cu single atom or dimer. Cu single-atom and Cun clusters (n = 2–4) doped into CeO2 all exhibit an excellent stability against ripening and a promising catalytic activity for low-temperature CO oxidation. This research for the first time elucidates the nature of CuxCe1-xO2 solid solution catalysts and paves the way for the rational design of Cu/CeO2 catalysts for CO oxidation.

The thermal transport, mechanical, and optical properties of T-Cu6S2: The influence of Cu6 clusters

Cluster substitution can effectively regulate the physicochemical properties of two-dimensional (2D) materials and has been applied in fields such as catalysis and magnetism. However, the intrinsic mechanism of its regulation of thermal transport properties and the impact of clusters on optical and mechanical properties are not yet clear. In this work, 2D T-Cu6S2 is obtained by replacing the transition metal element M of 2D T-MS2 with the Cu6 clusters. Then, based on the first-principles method, we systematically studied the thermal transport, mechanical, and optical properties of T-Cu6S2. The results show that introducing Cu6 clusters reduces the phonon vibration frequency, and enhances phonon scattering, that is, the coupling effect of harmonic weakening and anharmonic enhancement. This makes the lattice thermal conductivity of T-Cu6S2 at the four-photon level reduced to 0.18 W/mK (at 300 K), which is much lower than that of traditional 2D T-MS2. In addition, we found that the introduction of clusters changes the crystal and electronic structures of T-Cu6S2, enhances the flexibility and ductility of T-Cu6S2, and increases its transmission ability for visible light and ultraviolet light. This study provides insights into the regulation of multiple properties of 2D materials, which benefits the development of 2D functional materials.

Ab Initio Studies of Electrocatalytic CO2 Reduction for Small Cu Cluster Supported on Polar Substrates.

Small Cu clusters are excellent candidates for the electrocatalytic reduction of carbon dioxide (CO2RR), and their catalytic performance is expected to be significantly influenced by the interaction between the substrate and cluster. In this study, we systematically investigate the CO2RR for a Cu3 cluster anchored on Janus MoSX (X = Se, Te) substrates using density functional theory calculations. These substrates feature a broken vertical mirror symmetry, which generates spontaneous out-of-plane polarization and offers two distinct polar surfaces to support the Cu3 cluster. Our findings reveal that the CO2RR performance on the Cu3 cluster is strongly influenced by the polarization direction and strength of the MoSX (X = Se, Te) substrates. Notably, the Cu3 cluster supported on the S-terminated MoSTe surface (Cu3(S)@MoSTe) demonstrates the highest CO2RR activity, producing methane. These results underscore the pivotal role of substrate polarization in modulating the binding strength of reactants and reaction intermediates, thereby enhancing the CO2RR efficiency.

Electrocatalytic reduction of CO2 to C2H4 by monometallic Cu4 cluster supported on CeO2(110) surface

Cu-based catalysts have attracted much attention in the field of electrocatalytic CO2 reduction reactions (CRR). In our current work, the electrocatalytic reduction of CO2 by Cu cluster supported on CeO2 is calculated according to the density functional theory (DFT), and some interesting results are obtained. Monometallic copper cluster electrocatalysis of CO2 produce C2 products at lower potentials. The overpotential for the generation of ethylene is much lower than those of other products. The modulation of the substrate CeO2 changed the electronic structure of the Cu clusters and constructed Cu0 and Cu+1 active sites on the catalyst surface, and the coordinated action of Cu0 and Cu+1 made the C–C coupling more likely to take place and facilitated the generation of C2 products. The results of this study help to further understand the role of Cu-based catalysts in the electrocatalytic reduction of CO2 from theoretical point of view and provide guidance for future electrocatalytic experiments based on CRR.

Understanding the Decomposition of Dimethyl Methyl Phosphonate on Metal-Modified TiO2(110) Surfaces Using Ensembles of Product Configurations.

The decomposition of dimethyl methyl phosphonate (DMMP), a simulant for the nerve agent sarin, was investigated on Cu4/TiO2(110) and K/Cu4/TiO2(110) surfaces using a combination of near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and density functional theory calculations (DFT). Mass-selected Cu4 clusters and potassium (K) atoms were deposited onto TiO2(110) as a metal catalyst and alkali promoter to improve the reactivity and recyclability of the TiO2 surface after exposure to DMMP. Surface reaction products resulting from decomposition of DMMP were probed by NAP-XPS measurements of phosphorus (P) 2p and carbon 1s core-level spectra. The Cu4/TiO2(110) surface is found to be very active for DMMP decomposition with highly reduced P-species observed even at room temperature (RT). The codeposition of K atoms and Cu4 clusters further improves the reactivity with no intact DMMP detectable. Temperature-dependent measurements show that the presence of K atoms promotes the removal of residual P-species at temperatures > 600 K. Detailed DFT calculations were performed to determine the surface structures and energetically accessible pathways for DMMP decomposition on Cu4/TiO2(110) and K/Cu4/TiO2(110) surfaces. The calculations show that DMMP and P-containing reaction products preferentially bind to the TiO2 surface, while the molecular fragments, i.e., methoxy and methyl, bind to both the Cu4 clusters and TiO2. The Cu4 clusters make the P-O, O-C, and P-C bond cleavages of DMMP markedly more exothermic. The Cu4 clusters are highly fluxional with atomic structures that depend on the configuration of fragments bound to them. Finally, the manifold of P 2p chemical shifts calculated for a large number of energetically favorable configurations of decomposition products is in good agreement with the observed XPS spectra and provides an alternative way of interpreting incompletely resolved core-level spectra using an ensemble of observed structures.

Design and synthesis of different sized polyhedral channel MOF materials for the separation of CO2/N2

A fractal polyhedral pore structural MOFs (Cu-TATB) is synthesized from the coordination of tridentate ligands (H3TATB) and Cu4 clusters. This material is characterized by single crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis. The structure contains two different pore structures, including closed octahedral cages and open tetrakaidecahedron cages. The material has been successfully utilized for the separation of CO2/N2 due to the fractal structure of the channel with different pore sizes. Under optimized temperature, Cu-TATB adsorbed a large amount of CO2 and only negligible amount of N2, and the selectivity reaches 27. Breakthrough experiments demonstrated that this material can efficiently separate N2 and CO2. This structure further demonstrates the infinite potential of 3D MOFs with diverse pore structures in applications such as CO2 adsorption and separation.

Comparison of Cu3, Cu5, and Cu7 clusters as potential antioxidants: A theoretical quest.

Herein, we compare and contrast the dual roles of Cun clusters (n = 3, 5, and 7 atoms) in scavenging or generating RO• free radicals from ROH at the theoretical levels (where R = H, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, and phenyl). This investigation is performed in water media to mimic the actual environment in the biological system. In the presence of the Cun clusters, bond dissociation energy (BDE) of RO-H and R-OH is reduced. This is clear evidence for the increased possibility of both the RO-H and R-OH bonds breakage and scavenging of RO• radicals. The nature of anchoring bonds responsible for the interaction of Cun clusters with ROH and RO• are interpreted using the quantum theory of atoms in molecules (QTAIM) and the natural bond orbital (NBO) analysis. The DFT results indicate that the O•⋅⋅⋅•Cu bond is stronger and has more covalent character in RO•⋅⋅⋅•Cun radical complexes than in ROH⋅⋅⋅•Cun. Therefore, the interactions of Cun clusters with RO• radicals (antioxidant) are more pronounced than their interactions with ROH non-radicals (pro-oxidant). The GAMESS software package was utilized in this paper. The B3LYP and M06 functions with the 6-311 + + G(d,p), and LANL2DZ/SDD basis sets was used to perform the important geometrical parameters of RO•⋅⋅⋅•Cun and ROH⋅⋅⋅•Cun, binding energy (Eb), and bond dissociation energy (BDE).

Density functional theory study on the enhanced adsorption mechanism of VOCs by Cu4 cluster decorated UiO-66

Volatile organic compounds (VOCs) are a class of air pollutants that greatly harm human health and the ecological environment, convenient and effective treatment of VOCs has become a challenge. This work proposed a transition metal cluster decorated UiO-66 (a typical type of metal-organic framework) as the effective adsorbent for the purification of VOCs with typical functional groups based on density functional theory (DFT) calculations. The results show that the VOCs adsorption energy on the modified UiO-66 increased significantly, especially for Cu4 cluster-modified UiO-66, and the adsorption energy of trichloroethene is greater than that of the other considered VOCs, which may be induced by halogens or carbon-carbon double bond in trichloroethene. We compared chloromethane, chloroethylene, and ethylene and found that VOCs with carbon-carbon double bond have stronger adsorption energy, increasing with the number of chlorine atoms. The density of states (DOS), Hirshfeld charge analysis, and orbital distribution further confirm the charge distribution in UiO-66 after the decoration of the Cu4 cluster. Cu4 cluster can act as a bridge to promote the formation of chemical bonds between UiO-66 and VOCs molecules. Therefore, Cu4 cluster-modified UiO-66 can be a promising VOCs adsorption material, especially for vinyl chloride molecules.

Mechanistic insights into the CO2 reduction to ethylene catalyzed by F-modified Cu/graphene composites

Fluorine-modified copper catalysts are expected to improve electrocatalytic CO2 reduction performance. In addition to active species, the cluster/support interaction in cluster-loaded catalysts has been shown to vary according to both the inherent reactivity of the metal cluster and the properties of the support. Herein, Cu loaded fluorine-doped graphene catalyst (Cu/FDG) was designed and the mechanism of Cu/FDG-catalytic reduction of CO2 into ethylene were explored. F strengthens the interaction between Cu4 and graphene surface, promoting the electron transfer of Cu clusters to the fluorine-modified graphene due to the inductive effect, which results in the formation of both Cu0 and oxidized Cuδ+ species. These species hence accelerate the adsorption of *CO, while the *CO coupling favors the generation of ethylene on the top site of Cu4 cluster due to the undercoordinated environment. The electrophilic effect guiding interface charge population can be applied to tune the reaction selectivity of Cu-catalytic reduction of CO2.

N and OH-Immobilized Cu3 Clusters In Situ Reconstructed from Single-Metal Sites for Efficient CO2 Electromethanation in Bicontinuous Mesochannels.

Cu-based catalysts hold promise for electrifying CO2 to produce methane, an extensively used fuel. However, the activity and selectivity remain insufficient due to the lack of catalyst design principles to steer complex CO2 reduction pathways. Herein, we develop a concept to design carbon-supported Cu catalysts by regulating Cu active sites' atomic-scale structures and engineering the carbon support's mesoscale architecture. This aims to provide a favorable local reaction microenvironment for a selective CO2 reduction pathway to methane. In situ X-ray absorption and Raman spectroscopy analyses reveal the dynamic reconstruction of nitrogen and hydroxyl-immobilized Cu3 (N,OH-Cu3) clusters derived from atomically dispersed Cu-N3 sites under realistic CO2 reduction conditions. The N,OH-Cu3 sites possess moderate *CO adsorption affinity and a low barrier for *CO hydrogenation, enabling intrinsically selective CO2-to-CH4 reduction compared to the C-C coupling with a high energy barrier. Importantly, a block copolymer-derived carbon fiber support with interconnected mesopores is constructed. The unique long-range mesochannels offer an H2O-deficient microenvironment and prolong the transport path for the CO intermediate, which could suppress the hydrogen evolution reaction and favor deep CO2 reduction toward methane formation. Thus, the newly developed catalyst consisting of in situ constructed N,OH-Cu3 active sites embedded into bicontinuous carbon mesochannels achieved an unprecedented Faradaic efficiency of 74.2% for the CO2 reduction to methane at an industry-level current density of 300 mA cm-2. This work explores effective concepts for steering desirable reaction pathways in complex interfacial catalytic systems via modulating active site structures at the atomic level and engineering pore architectures of supports on the mesoscale to create favorable microenvironments.

An alternative catalytic cycle for selective methane oxidation to methanol with Cu clusters in zeolites.

The partial oxidation of methane to methanol catalyzed by Cu-exchanged zeolites involves at present a three-step procedure that requires changing reaction conditions along the catalytic cycle. In this work we present an alternative catalytic cycle for selective methane conversion to methanol using as active species small Cu5 clusters supported on CHA zeolite. Periodic DFT calculations show that molecular O2 is easily activated on Cu5 clusters producing bi-coordinated O atoms able to dissociate homolytically a CH bond from CH4 and to react with the radical-like non-adsorbed methyl intermediate formed producing methanol, while competitive overoxidation to CO2 is energetically disfavored. The present mechanistic study opens a new avenue to design catalytic materials based on their ability to stabilize radical species.

Theoretical study on electrocatalytic carbon dioxide reduction over copper with copper-based layered double hydroxides.

The conversion of CO2 into valuable fuels and multi-carbon chemical substances by electrical energy is an effective strategy to solve environmental problems by using renewable energy sources. In this work, the density functional theory (DFT) method is used to reveal the electrocatalytic mechanism of CO2 reduction reaction (CO2RR) over the surface of CuAl-Cl-layered double hydroxides (LDHs) with Cu monoatoms (Cu@CuAl-Cl-LDH), Cu2 diatoms (Cu2@CuAl-Cl-LDH), orthotetrahedral Cu4 clusters (Td-Cu4@CuAl-Cl-LDH) and planar Cu4 clusters (Pl-Cu4@CuAl-Cl-LDH). The active sites, density of states, adsorption energy, charge density difference and free energy are calculated. The results show that CO2RR over all the above five catalysts can generate C2 products. Pl-Cu4@CuAl-Cl-LDH tends to generate C2H5OH, while the remaining four structures all tend to produce C2H4. Cuδ+ favors CO2RR, and Td-Cu4@CuAl-Cl-LDH with a larger positively charged area at the active site has the better electrocatalytic performance among the calculated systems with a maximum step height of 0.78 eV. The selectivity of the products C2H4 and C2H5OH depends on the dehydration of the intermediate *C2H2O to *C2H3O or *CCH; if the dehydration produces *CCH intermediate, the final product is C2H4, and if no dehydration occurs, C2H5OH is produced. This work provides theoretical information and guidance for further rational design of efficient CO2RR catalysts for energy saving and emission reduction.