The electrochemical CO2 reduction reaction (CO2RR) is a promising approach for converting CO2 into valuable chemicals and promoting carbon cycling. Among the products of CO2RR, ethylene (C2H4), as a crucial chemical feedstock, holds significant market demand and economic value. The design of an electrolyte-free cathode in membrane electrode assemblies (MEAs) can effectively mitigate mass transfer limitations, reduce ohmic losses, and enhance interfacial efficiency, thereby significantly improving current density and product selectivity. The integration of copper-based catalysts into MEAs is considered a promising strategy for the industrial-scale production of C2H4 via CO2RR. However, comprehensive reviews on the application of copper-based catalysts in MEAs for CO2RR to C2H4 remain limited, particularly regarding systematic analyses of catalyst design strategies, optimization of MEA components and operating conditions, and MEA device configurations. This review systematically summarizes the latest research progress on copper-based catalysts in MEAs for CO2RR to C2H4. Firstly, the reaction mechanism of CO2RR to C2H4 was summarized and the role of intermediate adsorption regulation was highlighted in MEA systems. Secondly, strategies applied to optimize ethylene production using copper-based catalysts in MEAs were also summarized accordingly. Next, the influence of components, operational conditions, and device design for MEA was discussed. Finally, the opportunities and challenges of using copper-based catalysts in MEAs for C2H4 production were outlined. This review aims to provide insights and inspire further research efforts toward optimizing the performance of CO2RR to C2H4 in MEAs.
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Review Article
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Renewable-energy-driven nitrate (NO3−) electroreduction to ammonia (NH3) (NERA) has been an attractive technology for decarbonizing NH3 production and wastewater treatment. Improving NERA efficiency requires electrocatalysts that are earth-abundant and show fantastic performance. Here we report a semiempirical activity descriptor of eg occupancy (of surface B-site cations) for identifying inexpensive perovskite oxides with extremely high efficacy toward NERA. We establish the descriptor by systematic investigations of more than 10 perovskite oxides. These investigations demonstrate that their intrinsic NERA activities display a volcano-shaped dependence on eg occupancy and the optimized intrinsic activities are accessible at near-1 eg occupancies. This could plausibly be attributed to the favorable overlaps between surface adsorbates and vertically-oriented eg orbitals. More importantly, utilizing this descriptor, we predict a highly active, selective, and durable NERA electrocatalyst with a composition of Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF). Because of its close-to-1 eg occupancy (i.e. ~ 1.2), the BSCF features a superior NH3 production rate of 0.12 g·h−1·mgcat.−1 (Faradaic efficiency of 97.8%) that is at top of the volcano plot, and substantially outperforms most NERA electrocatalysts reported in literature.
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