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    电催化生物质基平台分子氧化耦合硝酸盐还原研究进展

    Research Progress on Electrocatalytic Oxidation of Biomass-Based Platform Molecules Coupled with Nitrate Reduction

    • 摘要: 生物质资源的高值化利用与含氮废水的绿色处理是实现“双碳”目标与循环经济的重要途径。电催化技术可在温和条件下将生物质基平台分子(如5-羟甲基糠醛、糠醛和乳酸)选择性氧化为高附加值化学品,同时耦合阴极硝酸盐还原反应合成氨,实现“以废治废”的协同增效。与已有综述对单一反应体系的报道不同,本文以热力学协同机制和双功能催化剂设计原则为核心视角,基于官能团特征与电子转移数的分类依据,对比分析三者反应机理与路径的本质差异,得出核心结论:阳极生物质氧化与阴极硝酸盐还原的适配性由电位匹配、pH适配和反应器构型三要素共同决定。本文首先系统综述了3种典型生物质基平台分子的电催化氧化反应路径、催化剂设计策略及机理研究进展,对比了三者在反应机理与反应路径方面的本质差异,并重点讨论了不同阳极氧化策略与阴极硝酸盐还原的适配性。其次,重点讨论了电催化硝酸盐还原的反应转化路径与催化剂设计策略。然后,深入分析了将阳极生物质基平台分子氧化与阴极硝酸盐还原耦合的热力学优势及当前研究进展。最后,从高效双功能催化剂开发和耦合体系适配性优化等方面对未来的研究方向进行了展望。

       

      Abstract: The high-value valorization of biomass-derived resources and the eco-friendly remediation of nitrogen-laden wastewater represent pivotal challenges for realizing dual-carbon targets and advancing the circular economy. Under mild operational conditions, an electrocatalysis strategy enables the conversion of biomass-derived platform molecules, namely 5-hydroxymethylfurfural, furfural, and lactic acid, into high-value fine chemicals (e.g., 2,5-furandicarboxylic acid and furoic acid). This anodic oxidation process can be coupled with cathodic nitrate reduction to synthesize valuable ammonia, thereby establishing a synergistic “waste treats waste” paradigm that substantially enhances resource utilization and economic viability. Unlike existing reviews that address discrete electrocatalytic reaction systems separately, this work focuses on thermodynamic synergy mechanisms and bifunctional catalyst design principles for coupled electrolytic systems. A central viewpoint is that anodic biomass oxidation is not merely an energy-saving alternative to the oxygen evolution reaction; rather, it functions as a modulable reaction unit that requires precise coordination with cathodic nitrate reduction in terms of molecular reactivity, electron transfer stoichiometry, and electrolyte microenvironment. This work systematically compares 5-hydroxymethylfurfural, furfural, and lactic acid as representative anodic substrates based on their functional group characteristics and oxidation extents. Specifically, 5-hydroxymethylfurfural undergoes a six-electron oxidation to 2,5-furandicarboxylic acid via intermediates such as 2,5-diformylfuran or 5-hydroxymethyl-2-furancarboxylic acid; furfural follows a two-electron oxidation pathway to furoic acid; and lactic acid proceeds via C—C bond cleavage to yield pyruvate, acetate, or fully oxidized species. This comparative analysis demonstrates that substrate molecular structure, pH-dependent chemical stability, intermediate transformation pathways, and catalyst-tunable pathway selectivity collectively determine the compatibility between anodic reactions and nitrate reduction. This review also elaborates on the reaction pathways and catalyst engineering strategies for electrocatalytic nitrate reduction. Comparative thermodynamic analysis, electrolyte condition screening, and electrode catalyst requirement assessment collectively indicate that the coupling of biomass oxidation and nitrate reduction is governed by three intercorrelated core variables: potential matching, pH compatibility, and reactor geometry. Potential matching dictates overall energy efficiency; pH compatibility regulates substrate stability, intermediate evolution, and catalyst durability; and reactor geometry controls mass transport, ion migration, and in-situ product separation. These three parameters constitute a universal evaluation framework for assessing the feasibility of integrating diverse anodic oxidation reactions with cathodic nitrate reduction. Future research should shift from the independent optimization of single-electrode performance toward holistic system-level integration. Promising directions include the design of bifunctional electrocatalysts with asymmetric active sites, intrinsic defects, heterointerfaces, or tandem catalytic centers to balance anodic and cathodic kinetics; evaluation of long-term durability in real nitrate-containing wastewater and crude biomass-derived feedstocks; and integration of techno-economic analysis with life-cycle assessment to identify practical pathways for green ammonia synthesis and biomass upgrading.

       

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