Electrocatalytic nitric oxide reduction reaction (NORR) for ammonia synthesis has emerged as a research focus in artificial nitrogen fixation. Unlike previous reviews that primarily focus on experimental catalyst development, this work offers a comprehensive and systematic summary of recent theoretical progress in NORR, with special emphasis on low-dimensional materials. We connect four important areas: atomic-level design principles for active sites, emerging mechanistic ideas that go beyond conventional scaling relations, realistic simulations of the electrochemical microenvironment, and data-driven machine learning approaches for catalyst discovery. We begin by discussing the reaction mechanism, analyzing the orbital interactions that control NO activation and the thermodynamic and kinetic features of different reaction pathways. For active-site construction, we examine electronic synergy in single-atom and dual-atom catalysts, coordination microenvironment tuning, electronic structure modulation through doping and strain, and heterojunction interfaces that allow multi-degree-of-freedom regulation. To explore new mechanistic concepts, we introduce p-block element synergy, reverse activation, magnetic and spin control, and surface electronic singularities as strategies to overcome traditional scaling relations. Regarding the reaction microenvironment, we analyze how coverage, solvation, local pH, and applied potential jointly affect selectivity and activity. Finally, we summarize the role of machine learning in building descriptors and accelerating catalyst screening. This review aims to provide theoretical guidance for the rational design of efficient NORR electrocatalysts with high activity, selectivity, and long-term stability.
The electrocatalytic reduction of nitrate to ammonia (NRA) presents a sustainable approach for ammonia production, yet the design of high-performance catalysts remains a formidable challenge. This review explores how the integration of density functional theory (DFT), machine learning (ML), and in situ characterization can accelerate the development of non-precious catalyst for NRA. By synergizing real-time experimental data, first-principles calculations, and data-driven models, these techniques establish a robust framework for unraveling complex structure–activity relationships and enhancing catalyst performance. ML facilitates rapid screening and prediction, while DFT offers detailed atomic-level insights into reaction mechanisms. in situ characterization, on the other hand, provides dynamic understanding of catalyst behavior under actual reaction conditions. The combination of these methods not only enables more rational catalyst design but also deepens our comprehension of the underlying core processes. This review summarizes recent advancements, discusses ongoing challenges, and outlines future directions for leveraging these integrated approaches to achieve efficient and scalable electrocatalytic nitrate-to-ammonia reduction using non-precious catalysts.
Syed Taj Ud Din, Xinhong Chen, Le-Yun Qi et al.· Chemical Physics Reviews· 0 citations
The electrocatalytic nitrogen reduction reaction (ENRR) offers a sustainable pathway for ammonia synthesis under mild conditions, yet its practical implementation is hindered by poor N2 activation efficiency and the lack of a clear structure-activity relationship for rational catalyst design. Herein, we systematically investigate the electrocatalytic performance of vacancy-engineered M2CT2 (M = Ti, Nb, and Mo; T = O, S, Cl, and Br) MXenes for the ENRR using well-defined density functional theory calculations combined with microkinetic modeling. Our results demonstrate that surface vacancies significantly modulate the local electronic structure of MXenes, thereby promoting N2 adsorption and activation. The results demonstrated that the ENRR proceeded on VT-M2CT2 through the distal pathway according to free energy calculations. A novel descriptor, Ψ, based on the valence of the transition metal and the lattice constant, is proposed to establish a quantitative structure-activity relationship, enabling rapid screening of high-performance catalysts. Among the candidates, vacancy-engineered Ti2CBr2 exhibits outstanding ENRR activity, as further validated by microkinetic analysis. This work provides a universal strategy for the design of defect-mediated MXene catalysts and paves the way for the development of efficient ENRR electrocatalysts.
Rong Chen, JunTao Jia, Hongbin Sun et al.· Physical Chemistry, Chemical...· 0 citations
Electrocatalytic carbon dioxide reduction reaction (CO2RR), driven by renewable energy sources, has provided a promising route to convert CO2 into value-added fuels and feedstocks for carbon neutrality. However, its selectivity and conversion efficiency are severely constrained by the chemical inertness of CO2, the complexity of reaction pathways, and the competing hydrogen evolution reaction, thus hindering widespread commercial deployments. Emerging research into atomically precise interfacial catalysis offers new opportunities to overcome these hurdles, enabling precise control over the reaction pathway and product selectivity. This review surveys recent advances in atomic-level interface engineering, focusing on the relationships among catalyst structure, reaction pathways, and CO2RR performance and mechanism. The rational design and construction of atomic-level catalytically active interfaces are highlighted, including strategies such as creating and modulating interfacial asymmetric sites, surface atomic arrangements, and reaction microenvironments. We also offer a forward-looking perspective on exploring these interfacial engineering approaches. We contend that understanding and harnessing interfacial effects through atomic-level catalyst modulation is central to advancing practical CO2RR technologies.
You-Zeng Li, Huan Wang, Ke Chen· The Catalyst· 0 citations
The electrochemical reduction of oxyanions offers a versatile and sustainable pathway for environmental remediation and the synthesis of value-added chemical feedstocks. This review provides a comprehensive analysis of the electrocatalytic conversion of a broad spectrum of oxyanions, including nitrate/nitrite, (bi)carbonate, bromate, perchlorate, (bi)chromate, and selenate/selenite. We highlight the progress in the typical used electrocatalysts and common mechanistic features that govern these reactions, such as multi-electron/proton transfer pathways, key intermediate adsorption, and competitive side processes, and discuss how mechanistic understanding can inform catalyst design. Particular emphasis is placed on the rational design of catalysts to simultaneously enhance activity, selectivity, and stability. We systematically evaluate engineering approaches to boost intrinsic activity, including increasing electrical conductivity and regulating electronic structures, and apparent activity, including exposing highly active facets, reducing the spatial dimensions of active sites, promoting H* generation and tailoring the interfacial microenvironment. To achieve precise product selectivity, we delineate fundamental principles focused on optimizing the adsorption energy for key intermediates, deliberately manipulating atom coupling pathways, and strictly inhibiting the competitive hydrogen evolution reaction. Furthermore, we summarize advanced strategies to address the critical challenge of long-term stability, encompassing both the intrinsic atomic-scale durability of active sites and systemic robustness under practical operational conditions. Finally, we outline emerging opportunities and future directions for developing next-generation electrocatalysts capable of operating at high current densities under practical conditions. This review aims to establish a consolidated mechanistic framework to accelerate the development of advanced catalytic platforms for the sustainable conversion of oxyanion pollutants and feedstocks.
Yuhan Liu, Cheng-Yan Gong, Chao Yuan et al.· Topics in current chemistry· 0 citations
In recent years, the electrocatalytic nitrate reduction reaction (eNitRR) has attracted growing interest in energy and environmental science. This technology enables the efficient and environmentally friendly synthesis of high-value ammonia (NH3). It can also remove nitrate from contaminated water. However, eNitRR exhibits slow kinetics, involving a variety of intermediates, different product types, and multiple reaction pathways. The hydrogen evolution reaction (HER) also competes with eNitRR for protons and electrons. These inherent challenges limit the efficient reduction of nitrates. Atomic doping engineering offers an effective strategy to address this problem. This review systematically discusses the mechanism of eNitRR and side reactions. In the section on the effects of doping on eNitRR, the mechanism by which doping regulates active sites is discussed from four perspectives: adsorption behavior, charge transfer, reaction pathways, and active site density, providing helpful guidance for the rational design of eNitRR catalysts. In addition, synthesis strategies for doped catalysts are summarized, along with recent progress in noble metal doping, non-noble metal doping, nonmetal doping, and codoping. This review also discusses opportunities and research directions for future development of doping engineering in eNitRR, aiming to provide useful guidance for the design of high-performance eNitRR catalysts.
Electrocatalytic nitrate (NO3 -) reduction reaction (eNO3RR) has emerged as a promising strategy for waste NO3 - valorization, offering opportunities for environmental remediation. However, its complex proton-coupled electron transfer processes involve multiple competing pathways, in which the fate of key intermediates governs reaction activity and product selectivity. In this review, we provide an intermediate-centered perspective on eNO3RR, covering the reaction pathways from NO3 - activation to the selective synthesis of NH3, N2, and NH2OH. We then summarize current techniques for probing N-containing intermediates and active hydrogen (*H). On this basis, we discuss how catalyst design and microenvironment engineering regulate key processes in eNO3RR, including intermediate adsorption, retention and desorption, N─O bond cleavage, hydrogenation, and N─N coupling. We also examine the emerging role of data-driven approaches in optimizing eNO3RR systems. Drawing these discussions together, we distill principles for selective product synthesis. Finally, we discuss remaining challenges in achieving a deeper mechanistic understanding, regulating the interfacial microenvironment, and applying eNO3RR to real wastewater.
Yingying Zhou, Jie Wu, Weisong Li et al.· Angewandte Chemie· 0 citations
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