Confined Growth of Silver–Copper Janus Nanostructures with {100} Facets for Highly Selective Tandem Electrocatalytic Carbon Dioxide Reduction

Abstract

Electrocatalytic carbon dioxide reduction reaction (CO2RR) holds significant potential to promote carbon neutrality. However, the selectivity toward multicarbon products in CO2RR is still too low to meet practical applications. Here the authors report the delicate synthesis of three kinds of Ag–Cu Janus nanostructures with {100} facets (JNS‐100) for highly selective tandem electrocatalytic reduction of CO2 to multicarbon products. By controlling the surfactant and reduction kinetics of Cu precursor, the confined growth of Cu with {100} facets on one of the six equal faces of Ag nanocubes is realized. Compared with Cu nanocubes, Ag65–Cu35 JNS‐100 demonstrates much superior selectivity for both ethylene and multicarbon products in CO2RR at less negative potentials. Density functional theory calculations reveal that the compensating electronic structure and carbon monoxide spillover in Ag65–Cu35 JNS‐100 contribute to the enhanced CO2RR performance. This study provides an effective strategy to design advanced tandem catalysts toward the extensive application of CO2RR.

Cu-Based Tandem Catalysts for Electrochemical CO₂ Reduction

“…It has been proven that Cu(100) facet is more conducive to the production of C2+ products due to its lower C-C coupling energy barrier, while Cu (111) facet tends to generate C1 products [136][137][138] . Therefore, when designing an (i) schematic illustration of a plausible CO2RR mechanism on Ag65-Cu35 JNS-100 140 .…”

“…Adapted from Springer Nature 125 , American Chemical Society 126,127,139 , Elsevier 133 and John Wiley and Sons 134,140 , respectively. advanced tandem catalyst, the effect of facets should also be considered.…”

“…In addition, the selectivity of the product C2H4 can likewise be enhanced by the combination of the facet effect and tandem catalysis. Ma et al 140 synthesized three kinds of Ag-Cu nanostructures with (100) facets. By controlling the surfactant and reduction kinetics of the Cu precursor, the authors achieved restricted growth of Cu with (100) facets on Ag.…”

Revealing the activity and selectivity of ppm level copper in gas diffusion electrodes towards CO and CO2 electroreduction

“…[16][17][18] Cu stands out as the only known metal catalyst capable of generating high-order products such as C 1 -C 2 hydrocarbons (e.g., CH 4 and C 2 H 4 ) and C 2+ oxygenates (e.g., CH 3 CH 2 OH, CH 3 COOH, and C 3 H 7 OH,) beyond the 2ereduction route. [19][20][21][22][23] Moreover, Cu is also the unique metal that catalyzes the electrochemical CO reduction reaction (CORR), a critical intermediate reaction in CO 2 RR, to form a similar distribution of C 2+ hydrocarbons and oxgenates. 24,25 A trace level of Cu nanoparticles (e.g., 119 ppm) in graphene oxide loaded on glass carbon substrate exhibited electrochemical activity toward CO 2 RR in an H-cell.…”

Electrocatalytic Reduction of Carbon Dioxide to High-Value Multicarbon Products with Metal–Organic Frameworks and Their Derived Materials

“…The heavy reliance of anthropogenic activities and industrialization on fossil fuels has dramatically increased the concentrations of atmospheric greenhouse gases, especially carbon dioxide (CO 2 ). − Growing concern in the areas of global warming, extreme weather, climate change, and energy crisis is driving research on efficient CO 2 conversion to achieve carbon neutrality. − Given the advantage of being able to be powered by renewable electricity, the electrocatalytic CO 2 reduction reaction (CO 2 RR) has emerged as one of the most promising and sustainable methods to convert CO 2 to valuable chemicals and fuels, especially highly valuable multicarbon (C 2+ ) products like ethylene (C 2 H 4 ), acetic acid (CH 3 COOH), ethanol (C 2 H 5 OH), and n-propanol ( n -C 3 H 7 OH). − Among various types of electrocatalysts, copper (Cu)-based materials exhibited the most efficient electrochemical CO 2 conversion toward C 2+ products. − To date, great effort, such as composition regulation, − morphology adjustment, , defect control, − strain modulation, , and phase engineering, − has been devoted to modulating Cu-based electrocatalysts to boost the C 2+ production in CO 2 RR. However, due to the multiple electron-transfer processes and competitive reactions, it is still challenging to regulate the CO 2 RR reaction pathway toward C 2+ products. − Meanwhile, most CO 2 RR electrocatalysts still demonstrate inferior activity, poor selectivity and low stability that limit the industry-scale applications. − Hence, it is critically important to explore novel high-performance CO 2 RR electrocatalysts to efficiently convert CO 2 molecules to C 2+ products.…”