Heterogeneous catalysis plays an important role in modern industries. Exploring catalysts with high efficiency, low-cost and high stability is an important issue for the research of heterogeneous c...

Defect chemistry in heterogeneous catalysis: recognition, understanding and utilization

Compared to modern fossil-fuel-based refineries, the emerging electrocatalytic refinery (e-refinery) is a more sustainable and environmentally benign strategy to convert renewable feedstocks and energy sources into transportable fuels and value-added chemicals. A crucial step in conducting e-refinery processes is the development of appropriate reactions and optimal electrocatalysts for efficient cleavage and formation of chemical bonds. However, compared to well-studied primary reactions (e.g., O2 reduction, water splitting), the mechanistic aspects and materials design for emerging complex reactions are yet to be settled. To address this challenge, herein, we first present fundamentals of heterogeneous electrocatalysis and some primary reactions, and then implement these to establish the framework of e-refinery by coupling in situ generated intermediates (integrated reactions) or products (tandem reactions). We also present a set of materials design principles and strategies to efficiently manipulate the reaction intermediates and pathways.

Electrocatalytic Refinery for Sustainable Production of Fuels and Chemicals

Transformation technologies for CO2 utilisation: Current status, challenges and future prospects

Electrochemical reduction of gaseous feeds such as CO2, CO, and N2 holds promise for sustainable energy and chemical production. Practical application of this technology is impeded by slow mass transport of the sparingly soluble gases to conventional planar electrodes. Gas diffusion electrodes (GDEs) maintain a high gas concentration in the vicinity of the catalyst and improve mass transport, thereby resulting in current densities higher by orders of magnitude. However, gaseous feeds cause changes to the GDE environment, and specific features are required to efficiently tune the product selectivity and improve reaction stability. Herein, with a comprehensive review of the challenges and advances in GDE development for various electrocatalytic reactions, we intend to complement the body of material-focused reviews. This review outlines GDE fundamentals and highlights key advantages of GDE over conventional electrodes. Through critical discussion about steps in GDE fabrication, and specific shortcomings and remedial strategies for various electrochemical applications, this review discusses connections, unique design criteria, and potential opportunities for gas-fed reactions and desired products. Finally, priorities for future studies are suggested, to support the advancement and scale-up of GDE-based electrochemical technologies.

Gas diffusion electrodes (GDEs) for electrochemical reduction of carbon dioxide, carbon monoxide, and dinitrogen to value-added products: a review

Nitrate enrichment, which is mainly caused by the over-utilization of fertilisers and industrial sewage discharge, is a major global engineering challenge because of its negative influence on the environment and human health. To solve this serious problem, many technologies, such as the activated sludge method, reverse osmosis, ion exchange, adsorption, and electrodialysis, have been developed to reduce the nitrate levels in water bodies. However, the applications of these traditional techniques are limited by several drawbacks, such as a long sludge retention time, slow kinetics, and undesirable by-products. From an environmental perspective, the most promising nitrate reduction technology is enabled to convert nitrate into benign N2, and features low cost, high efficiency, and environmental friendliness. Recently, electrocatalytic nitrate reduction has been proven by satisfactory research achievements to be one of the most promising methods among these technologies. This review provides a comprehensive account of nitrate reduction using electrocatalysis methods. The fundamentals of electrocatalytic nitrate reduction, including the reaction mechanisms, reactor design principles, product detection methods, and performance evaluation methods, have been systematically summarised. A detailed introduction to electrocatalytic nitrate reduction on transition metals, especially noble metals and alloys, Cu-based electrocatalysts, and Fe-based electrocatalysts is provided, as they are essential for the accurate reporting of experimental results. The current challenges and potential opportunities in this field, including the innovation of material design systems, value-added product yields, and challenges for products beyond N2 and large-scale sewage treatment, are highlighted.

Electrocatalytic reduction of nitrate - a step towards a sustainable nitrogen cycle.

The use of nitrogen fertilizers has been estimated to have supported 27% of the world’s population over the past century. Urea (CO(NH2)2) is conventionally synthesized through two consecutive industrial processes, N2 + H2 → NH3 followed by NH3 + CO2 → urea. Both reactions operate under harsh conditions and consume more than 2% of the world’s energy. Urea synthesis consumes approximately 80% of the NH3 produced globally. Here we directly coupled N2 and CO2 in H2O to produce urea under ambient conditions. The process was carried out using an electrocatalyst consisting of PdCu alloy nanoparticles on TiO2 nanosheets. This coupling reaction occurs through the formation of C–N bonds via the thermodynamically spontaneous reaction between *N=N* and CO. Products were identified and quantified using isotope labelling and the mechanism investigated using isotope-labelled operando synchrotron-radiation Fourier transform infrared spectroscopy. A high rate of urea formation of 3.36 mmol g–1 h–1 and corresponding Faradic efficiency of 8.92% were measured at –0.4 V versus reversible hydrogen electrode. Conventionally, urea is synthesized via two consecutive processes, N2 + H2 → NH3 followed by NH3 + CO2. Now, an electrocatalyst consisting of PdCu alloy nanoparticles on TiO2 nanosheets has been shown to directly couple N2 and CO2 in H2O to produce urea under ambient conditions.

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Jun Cheng

Papers

Coupling N2 and CO2 in H2O to synthesize urea under ambient conditions