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Electroreduction of CO2 to C2+ products provides a promising strategy for reaching the goal of carbon neutrality. However, achieving high selectivity of C2+ products at high current density remains a challenge. In this work, we designed and prepared a multi‐sites catalyst, in which Pd was atomically dispersed in Cu (Pd−Cu). It was found that the Pd−Cu catalyst had excellent performance for producing C2+ products from CO2 electroreduction. The Faradaic efficiency (FE) of C2+ products could be maintained at approximately 80.8 %, even at a high current density of 0.8 A cm−2 for at least 20 hours. In addition, the FE of C2+ products was above 70 % at 1.4 A cm−2. Experiments and density functional theory (DFT) calculations revealed that the catalyst had three distinct catalytic sites. These three active sites allowed for efficient conversion of CO2, water dissociation, and CO conversion, ultimately leading to high yields of C2+ products. [ABSTRACT FROM AUTHOR]

Catalytic conversion of CO2 to produce fuels and chemicals is of great importance, and the electrocatalytic CO2 reduction reaction (eCO2RR) is considered one of the most attractive pathways. Multi-carbon (C2+) products are more desirable in many cases. To date, Cu-based catalysts, especially Cu+ sites, have been found to be the most efficient for the production of C2+ products. However, the retention of Cu+ sites at high cathodic potentials in the eCO2RR remains a great challenge. In this study, we designed and synthesized CuAl-oxide-derived (CuxAly-OD, x and y are the mass percentages of Cu and Al) catalysts for the eCO2RR to C2+ products. During the eCO2RR process, the predominant Cu species changed to Cu+, and the resulting electrocatalyst showed a high faradaic efficiency (FE) of 81.6% for C2+ products in alkaline aqueous solutions. Experimental studies showed that the presence of a stable amorphous Al2O3 phase stabilized the Cu+ sites by oxidation state control, leading to high selectivity and activity for the production of C2+ products. This work provides a strategy for improving the stability of Cu+ in the catalyst to enhance the performance of the eCO2RR. [ABSTRACT FROM AUTHOR]

Electroreduction of CO2 into valuable chemicals and fuels is a promising strategy to mitigate energy and environmental problems. However, it usually suffers from unsatisfactory selectivity for a single product and inadequate electrochemical stability. Herein, we report the first work to use cationic Gemini surfactants as modifiers to boost CO2 electroreduction to formate. The selectivity, activity and stability of the catalysts can be all significantly enhanced by Gemini surfactant modification. The Faradaic efficiency (FE) of formate could reach up to 96 %, and the energy efficiency (EE) could achieve 71 % over the Gemini surfactants modified Cu electrode. In addition, the Gemini surfactants modified commercial Bi2O3 nanosheets also showed an excellent catalytic performance, and the FE of formate reached 91 % with a current density of 510 mA cm−2 using the flow cell. Detailed studies demonstrated that the double quaternary ammonium cations and alkyl chains of the Gemini surfactants played a crucial role in boosting electroreduction CO2, which can not only stabilize the key intermediate HCOO* but also provide an easy access for CO2. These observations could shine light on the rational design of organic modifiers for promoted CO2 electroreduction. [ABSTRACT FROM AUTHOR]

Modulation of the microenvironment on the electrode surface is one of the effective means to improve the efficiency of electrocatalytic carbon dioxide reduction (eCO2RR). To achieve high conversion rates, the phase boundary at the electrode surface should be finely controlled to overcome the limitation of CO2 solubility in the aqueous electrolyte. Herein, we developed a simple and efficient method to structure electrocatalyst with a superhydrophobic surface microenvironment by one‐step co‐electrodeposition of Cu and polytetrafluoroethylene (PTFE) on carbon paper. The super‐hydrophobic Cu‐based electrode displayed a high ethylene (C2H4) selectivity with a Faraday efficiency (FE) of 67.3 % at −1.25 V vs. reversible hydrogen electrode (RHE) in an H‐type cell, which is 2.5 times higher than a regular Cu electrode without PTFE. By using PTFE as a surface modifier, the activity of eCO2RR is enhanced and water (proton) adsorption is inhibited. This strategy has the potential to be applied to other gas‐conversion electrocatalysts. [ABSTRACT FROM AUTHOR]

Electrochemical reduction reaction of carbon monoxide (CORR) offers a promising way to manufacture acetic acid directly from gaseous CO and water at mild condition. Herein, we discovered that the graphitic carbon nitride (g‐C3N4) supported Cu nanoparticles (Cu−CN) with the appropriate size showed a high acetate faradaic efficiency of 62.8 % with a partial current density of 188 mA cm−2 in CORR. In situ experimental and density functional theory calculation studies revealed that the Cu/C3N4 interface and metallic Cu surface synergistically promoted CORR into acetic acid. The generation of pivotal intermediate −*CHO is advantage around the Cu/C3N4 interface and migrated *CHO facilitates acetic acid generation on metallic Cu surface with promoted *CHO coverage. Moreover, continuous production of acetic acid aqueous solution was achieved in a porous solid electrolyte reactor, indicating the great potential of Cu−CN catalyst in the industrial application. [ABSTRACT FROM AUTHOR]

Amorphous nano-metal catalysts often exhibit appealing catalytic properties, because the intrinsic linear scaling relationship can be broken. However, accurate control synthesis of amorphous nano-metal catalysts with desired size and morphology is a challenge. In this work, we discover that Cu(0) could be oxidized to amorphous CuxO species by supercritical CO2. The formation process of the amorphous CuxO is elucidated with the aid of machine learning. Based on this finding, a method to prepare Cu nanoparticles with an amorphous shell is proposed by supercritical CO2 treatment followed by electroreduction. The unique feature of this method is that the size of the particles with amorphous shell can be easily controlled because their size depends on that of the original crystal Cu nanoparticles. Moreover, the thickness of the amorphous shell can be easily controlled by CO2 pressure and/or treatment time. The obtained amorphous Cu shell exhibits high selectivity for C2+ products with the Faradaic efficiency of 84% and current density of 320 mA cm−2. Especially, the FE of C2+ oxygenates can reach up to 65.3 %, which is different obviously from the crystalline Cu catalysts. Amorphous metal catalysts often exhibit appealing catalytic properties, however, accurate control synthesis of amorphous nano-metal catalysts is a challenge. Here, the authors report a feasible strategy to prepare the amorphous Cu catalysts by supercritical CO2 treatment followed by electroreduction. The resulted catalyst shows high selectivity towards multi-carbon products for CO2 electroreduction. [ABSTRACT FROM AUTHOR]

Methanol is a highly desirable product of CO2 electroreduction due to its wide array of industrial applications. However, the development of CO2-to-methanol electrocatalysts with high performance is still challenging. Here we report an operationally simple in situ dual doping strategy to construct efficient CO2-to-methanol electrocatalysts. In particular, when using Ag,S-Cu2O/Cu as electrocatalyst, the methanol Faradaic efficiency (FE) could reach 67.4% with a current density as high as 122.7 mA cm−2 in an H-type cell using 1-butyl-3-methylimidazolium tetrafluoroborate/H2O as the electrolyte, while the current density was below 50 mA cm−2 when the FE was greater than 50% over the reported catalysts. Experimental and theoretical studies suggest that the anion S can effectively adjust the electronic structure and morphology of the catalysts in favor of the methanol pathway, whereas the cation Ag suppresses the hydrogen evolution reaction. Their synergistic interactions with host material enhance the selectivity and current density for methanol formation. This work opens a way for designing efficient catalysts for CO2 electroreduction to methanol. Production of methanol from CO2 electroreduction is attractive but achieving high selectivity, current density and stability simultaneously remains a grand challenge. Here, the authors present an in situ dual doping strategy to construct efficient CO2-to-methanol electrocatalysts. [ABSTRACT FROM AUTHOR]

Developing electrocatalytic reactions with high‐efficiency can make important contributions to carbon neutrality. However, poor long‐term stability of catalysts is a bottleneck for its practical application. Herein, an "in situ periodic regeneration of catalyst (PR‐C)" strategy is proposed to give long‐term high efficiency of CO2 electroreduction to generate C2+ products over Cu catalyst by applying a positive potential pulse for a short time periodically in the halide‐containing electrolyte. The high Faradaic efficiency (81.2 %) and current density (22.6 mA cm−2) could be maintained completely at least 36 h, while the activity and selectivity decreased continuously without using the PR‐C method. Control experiments and operando characterization demonstrated that the surface structure and oxidation state of Cu could be recovered periodically by the PR‐C method, which was beneficial for CO2 activation and C−C coupling. [ABSTRACT FROM AUTHOR]

Electroreduction of CO2 into valuable fuels and feedstocks offers a promising way for CO2 utilization. However, the commercialization is limited by the low productivity. Here, we report a strategy to enhance the productivity of CO2 electroreduction by improving diffusion of CO2 to the surface of catalysts using porous organic cages (POCs) as an additive. It was noted that the Faradaic efficiency (FE) of C2+ products could reach 76.1 % with a current density of 1.7 A cm−2 when Cu‐nanorod(nr)/CC3 (one of the POCs) was used, which were much higher than that using Cu‐nr. Detailed studies demonstrated that the hydrophobic pores of CC3 can adsorb a large amount of CO2 for the reaction, and the diffusion of CO2 in the CC3 to the nanocatalyst surface is easier than that in the liquid electrolyte. Thus, more CO2 molecules make contact with the nanocatalysts in the presence of CC3, enhancing CO2 reduction and inhibiting generation of H2. [ABSTRACT FROM AUTHOR]

Electrochemical reduction of CO2 by renewable electricity offers a promising way to settle excessive greenhouse gases and achieve carbon neutrality under a mild environment. Cu-based catalysts have a unique catalytic activity towards multicarbon (C2+) products in the CO2 electroreduction reaction and are widely studied to promote the corresponding selectivity and activity. Here we report a F-doped Cu (F–Cu) catalyst to improve C2+ products in CO2 electroreduction. A high C2+ product (mainly ethylene and ethanol) faradaic efficiency of 70.4% was achieved on the F–Cu catalyst with a high current density (above 400 mA cm−2) in the flow-cell system. The in situ surface enhanced Raman spectroscopy results and electrochemical performance analysis demonstrated that CO2 could be reduced into CO at low potentials and the adsorption of CO could be strengthened on F–Cu, which is beneficial to the subsequent C–C coupling step and formation of the C2+ products. [ABSTRACT FROM AUTHOR]

Using renewable electricity to drive CO2 electroreduction is an attractive way to achieve carbon‐neutral energy cycle and produce value‐added chemicals and fuels. As an important platform molecule and clean fuel, methanol requires 6‐electron transfer in the process of CO2 reduction. Currently, CO2 electroreduction to methanol suffers from poor efficiency and low selectivity. Herein, we report the first work to design atomically dispersed Sn site anchored on defective CuO catalysts for CO2 electroreduction to methanol. It exhibits high methanol Faradaic efficiency (FE) of 88.6 % with a current density of 67.0 mA cm−2 and remarkable stability in a H‐cell, which is the highest FE(methanol) with such high current density compared with the results reported to date. The atomic Sn site, adjacent oxygen vacancy and CuO support cooperate very well, leading to higher double‐layer capacitance, larger CO2 adsorption capacity and lower interfacial charge transfer resistance. Operando experiments and density functional theory calculations demonstrate that the catalyst is beneficial for CO2 activation via decreasing the energy barrier of *COOH dissociation to form *CO. The obtained key intermediate *CO is then bound to the Cu species for further reduction, leading to high selectivity toward methanol. [ABSTRACT FROM AUTHOR]

Guided by first‐principles calculations, it was found that Cd single‐atom catalysts (SACs) have excellent performance in activating CO2, and the introduction of axial coordination structure to Cd SACs cannot only further decrease the free energy barrier of CO2 reduction, but also suppress the hydrogen evolution reaction (HER). Based on the above discovery, we designed and synthesized a novel Cd SAC that comprises an optimized CdN4S1 moiety incorporated in a carbon matrix. It was shown that the catalyst exhibited outstanding performance in CO2 electroreduction to CO. The faradaic efficiency (FE) of CO could reach up to 99.7 % with a current density of 182.2 mA cm−2 in a H‐type electrolysis cell, and the turnover frequency (TOF) value could achieve 73000 h−1, which was much higher than that reported to date. This work shows a successful example of how to design highly efficient catalysts guided by theoretical calculations. [ABSTRACT FROM AUTHOR]