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Tuning the selectivity of CO2 electroreduction reaction (CO2RR) solely by changing electrolyte is a very attractive topic. In this study, we conducted CO2RR in different aqueous electrolytes over bulk metal electrodes. It was discovered that controlled CO2RR could be achieved by modulating cations in the electrochemical double layer. Specifically, ionic liquid cations in the electrolyte significantly inhibits the hydrogen evolution reaction (HER), while yielding high Faraday efficiencies toward CO (FECO) or formate (FEformate) depending on the alkali metal cations. For example, the product could be switched from CO (FECO=97.3 %) to formate (FEformate=93.5 %) by changing the electrolyte from 0.1 M KBr‐0.5 M 1‐octyl‐3‐methylimidazolium bromide (OmimBr) to 0.1 M CsBr‐0.5 M OmimBr aqueous solutions over pristine Cu foil electrode. In situ spectroscopy and theoretical calculations reveal that the ordered structure generated by the assembly of Omim+ under an applied negative potential alters the hydrogen bonding structure of the interfacial water, thereby inhibiting the HER. The difference in selectivity in the presence of different cations is attributed to the hydrogen bonding effect caused by Omim+, which alters the solvated structure of the alkali metal cations and thus affects the stabilization of intermediates of different pathways. [ABSTRACT FROM AUTHOR]

Regulating the binding effect between the surface of an electrode material and reaction intermediates is essential in highly efficient CO2 electro‐reduction to produce high‐value multicarbon (C2+) compounds. Theoretical study reveals that lattice tensile strain in single‐component Cu catalysts can reduce the dipole–dipole repulsion between *CO intermediates and promotes *OH adsorption, and the high *CO and *OH coverage decreases the energy barrier for C−C coupling. In this work, Cu catalysts with varying lattice tensile strain were fabricated by electro‐reducing CuO precursors with different crystallinity, without adding any extra components. The as‐prepared single‐component Cu catalysts were used for CO2 electro‐reduction, and it is discovered that the lattice tensile strain in Cu could enhance the Faradaic efficiency (FE) of C2+ products effectively. Especially, the as‐prepared CuTPA catalyst with high lattice tensile strain achieves a FEC2+ of 90.9 % at −1.25 V vs. RHE with a partial current density of 486.1 mA cm−2. [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]

Upcycling of CO2 into fuels by virtually unlimited solar energy provides an ultimate solution for addressing the substantial challenges of energy crisis and climate change. In this work, we report an efficient nanostructured Ru/MnOx catalyst composed of well-defined Ru/MnO/Mn3O4 for photo-thermal catalytic CO2 hydrogenation to CH4, which is the result of a combination of external heating and irradiation. Remarkably, under relatively mild conditions of 200 °C, a considerable CH4 production rate of 166.7 mmol g−1 h−1 was achieved with a superior selectivity of 99.5% at CO2 conversion of 66.8%. The correlative spectroscopic and theoretical investigations suggest that the yield of CH4 is enhanced by coordinating photon energy with thermal energy to reduce the activation energy of reaction and promote formation of key intermediate COOH* species over the catalyst. This work opens up a new strategy for CO2 hydrogenation toward CH4. Reduction of CO2 with solar energy is an attractive route to new fuel sources. Here a nanostructured Ru/MnOx photo-thermal catalyst composed of well-defined Ru/MnO/Mn3O4 is reported for CO2 hydrogenation with high selectivity and a CH4 production rate at a mild temperature of 200 °C. [ABSTRACT FROM AUTHOR]

Electrocatalytic CO2 reduction (ECR) offers an attractive approach to realizing carbon neutrality and producing valuable chemicals and fuels using CO2 as the feedstock. However, the lack of cost-effective electrocatalysts with better performances has seriously hindered its application. Herein, a one-step co-electrodeposition method was used to introduce Zn, a metal with weak *CO binding energy, into Cu to form Cu/Zn intermetallic catalysts (Cu/Zn IMCs). It was shown that, using an H-cell, the high Faradaic efficiency of C2+ hydrocarbons/alcohols (FE C 2 + ) could be achieved in ECR by adjusting the surface metal components and the applied potential. In suitable conditions, FEC2+ and current density could be as high as 75% and 40 mA/cm2, respectively. Compared with the Cu catalyst, the Cu/Zn IMCs have a lower interfacial charge transfer resistance and a larger electrochemically active surface area (ECSA), which accelerate the reaction. Moreover, the *CO formed on Zn sites can move to Cu sites due to its weak binding with *CO, and thus enhance the C–C coupling on the Cu surface to form C2+ products. [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]

The electrochemical CO2 reduction reaction (CO2RR) presents a promising approach for producing valuable chemicals and fuels, offering a dual benefit in terms of environmental preservation and the efficient utilization of carbon resources. In this work, we proposed a stepwise electrodeposition method to prepare Cu−Pb bimetallic heterojunction catalyst on polyaniline‐modified carbon paper (PANI‐CuPb‐x), where x is the electrodeposition times(min). Among the studied catalysts, the electrode electrodeposited for 2 min (PANI‐CuPb‐2) exhibited a remarkable performance during the electrocatalysis CO2 to multicarbon (C2+) products process, achieving a Faraday efficiency (FE) of 81.46 % and a partial current density of 15.41 mA cm−2 at −1.2 V (vs. RHE) in an H‐type cell. The detailed study demonstrated that introducing Pb could effectively improve the formation of COOH*inhibit hydrogen evolution reaction (HER). Furthermore, the heterojunction structure in the catalysts facilitated C−C coupling of the generated C1 intermediate species, which enhanced the CO2 to C2+ reaction. [ABSTRACT FROM AUTHOR]

Waste residue of Chinese prickly ash seeds were simply treated with aqueous ZnCl2 to prepared the high-performed activated carbon. It was characterized by the methods of XRD, SEM, EDX, FT-IR, BET and XPS. The synergetic adsorption performance of Chinese prickly ash seeds activated carbon for Pb2+, Ni2+ and Acid Orange IΙ (AO) was studied. In the single-component system, the adsorption capacity of Pb2+, Ni2+ and AO were 15.1, 10.7 and 188.4 mg/g, respectively. In the AO-Pb2+ system, the maximum adsorption capacity of Pb2+ and AO were 79.40 and 332.68 mg/g under temperature of 30°C and pH of 5.0, respectively. For AO-Ni2+ system, it was 375.6 and 38.3 mg/g, respectively. The adsorption kinetics was satisfactorily fitted by the pseudo-second-order model. The synergic adsorption process can be smoothly described by the non-modified Sips isotherm. [ABSTRACT FROM AUTHOR]

Modulating the surface microenvironment of electrodes stands as a pivotal aspect in enhancing the electrocatalytic performance for CO2 electroreduction. Herein, we propose an innovative approach by incorporating a small amount of linear oligomer, polyethylene glycol (PEG), into Cu2O catalysts during the preparation of the CuPEG electrode. The Faradaic efficiency (FE) toward multicarbon products (C2+) increases from 69.3% over Cu electrode without PEG to 90.3% over CuPEG electrode at 500 mA cm-2 in 1 M KOH in a flow cell. In situ investigations and theoretical calculations reveal that PEG molecules significantly modify the microenvironment on the Cu surface through hydrogen bond interactions. This modification leads to the relaxation of Nafion, increasing the availability of active sites and enhancing the adsorption of *CO and *OH, which in turn promotes C-C coupling. Concurrently, the reconstructed hydrogen bond network reduces the presence of active hydrogen species, thereby inhibiting the hydrogen evolution reaction., (© 2025 Wiley‐VCH GmbH.)

Cu-based catalysts are optimal for the electroreduction of CO 2 to generate hydrocarbon products. However, controlling product distribution remains a challenging topic. The theoretical investigations have revealed that the coordination number (CN) of Cu considerably influences the adsorption energy of *CO intermediates, thereby affecting the reaction pathway. Cu catalysts with different CNs were fabricated by reducing CuO precursors via cyclic voltammetry (Cyc-Cu), potentiostatic electrolysis (Pot-Cu), and pulsed electrolysis (Pul-Cu), respectively. High-CN Cu catalysts predominantly generate C 2+ products, while low-CN Cu favors CH 4 production. For instance, over the high-CN Pot-Cu, C 2+ is the main product, with the Faradaic efficiency (FE) reaching 82.5% and a partial current density ( j ) of 514.3 mA cm -2 . Conversely, the low-CN Pul(3)-Cu favors the production of CH 4 , achieving the highest FE CH4 value of 56.7% with a j CH4 value of 234.4 mA cm -2 . In situ X-ray absorption spectroscopy and Raman spectroscopy studies further confirm the different *CO adsorptions over Cu catalysts with different CN, thereby directing the reaction pathway of the CO 2 RR.

Cu 2+ -based materials, a class of promising catalysts for the electrocatalytic carbon dioxide reduction reaction (CO 2 RR) to value-added chemicals, usually undergo inevitable and uncontrollable reorganization processes during the reaction, resulting in catalyst deactivation or the new active sites formation and bringing great challenges to exploring their structure-performance relationships. Herein, a facile strategy is reported for constructing Cu 2+ and 3, 4-ethylenedioxythiophene (EDOT) coordination to stabilize Cu 2+ ions to prepare a novel layered coordination polymer (CuPEDOT). CuPEDOT enables selective reduction of CO 2 to CH 4 with 62.7% Faradaic efficiency at the current density of 354 mA cm -2 in a flow cell, and the catalyst is stable for at least 15 h. In situ spectroscopic characterization and theoretical calculations reveal that CuPEDOT catalyst can maintain the Cu 2+ -EDOT coordination structurally stable in CO 2 RR and significantly promote the further hydrogenation of *CO intermediates, favoring the formation of CH 4 instead of dimerization to C 2 products. The strong coordination between EDOT and Cu 2+ prevents the reduction of Cu 2+ ions during CO 2 RR. The finding of this work provides a new perspective on designing molecularly stable, highly active catalysts for CO 2 RR., (© 2023 Wiley-VCH GmbH.)

The electrochemical reduction of carbon dioxide (CO 2 RR) holds great promise for sustainable energy utilization and combating global warming. However, progress has been impeded by challenges in developing stable electrocatalysts that can steer the reaction toward specific products. This study proposes a carbon shell coating protection strategy by an efficient and straightforward approach to prevent electrocatalyst reconstruction during the CO 2 RR. Utilizing a copper-based metal-organic framework as the precursor for the carbon shell, we synthesized carbon shell-coated electrocatalysts, denoted as Cu- x-y , through calcination in an N 2 atmosphere (where x and y represent different calcination temperatures and atmospheres: N 2 , H 2 , and NH 3 ). It was found that the faradaic efficiency of ethanol over the catalysts with a carbon shell could reach ∼67.8%. In addition, the catalyst could be stably used for more than 16 h, surpassing the performance of Cu-600-H 2 and Cu-600-NH 3 . Control experiments and theoretical calculations revealed that the carbon shell and Cu-C bonds played a pivotal role in stabilizing the catalyst, tuning the electron environment around Cu atoms, and promoting the formation and coupling process of CO*, ultimately favoring the reaction pathway leading to ethanol formation. This carbon shell coating strategy is valuable for developing highly efficient and selective electrocatalysts for the CO 2 RR., Competing Interests: The authors declare no competing interests., (This journal is © The Royal Society of Chemistry.)

Using bulk metals as catalysts to get high efficiency in electro-reduction of CO 2 is ideal but challenging. Here, we report the coupling of bulk metal electrodes and a ternary ionic-liquid-based electrolyte, 1-butyl-3-methylimidazolium tetrafluoroborate/1-dodecyl-3-methylimidazolium tetrafluoroborate/MeCN to realize highly efficient electro-reduction of CO 2 to CO. Over various bulk metal electrodes, the ternary electrolyte not only increases the current density but also suppresses the hydrogen evolution reaction to obtain a high Faradaic efficiency (FE) toward CO. FE CO could maintain ∼100% over a wide potential range, and metal electrodes showed very high stability in the ternary electrolyte. It is demonstrated that the aggregation behavior of the ternary electrolyte and the arrangement of two kinds of IL cations with different chain lengths in the electrochemical double layer not only increase the wettability to electrode and CO 2 adsorption but also extend the diffusion channel of H + , rendering the high current density and FE CO .