能量梯度匹配驱动催化级联实现协同硝酸盐电还原制氨

doi:10.1016/S1872-2067(26)65150-9

催化学报 ›› 2026, Vol. 90: 287-297.DOI: 10.1016/S1872-2067(26)65150-9

能量梯度匹配驱动催化级联实现协同硝酸盐电还原制氨

王智浩, 张宇昂, 张旭, 姜雨婷, 李欣悦, 谢颖, 任志宇, 陈志敏^*()

黑龙江大学化学化工与材料学院, 功能无机材料化学教育部重点实验室, 黑龙江哈尔滨 150080

收稿日期:2026-01-26 接受日期:2026-03-11 出版日期:2026-11-18 发布日期:2026-09-09
通讯作者: *电子信箱: zmchen@hlju.edu.cn (陈志敏).
基金资助:
国家自然科学基金(22179035);黑龙江省自然科学基金联合基金培育项目(PL2024B012);黑龙江省省属高校基本科研业务费(2023-KYYWF-1440)

Gradient energy alignment drives catalytic cascades for synergistic nitrate-to-ammonia electro-conversion

Zhihao Wang, Yuang Zhang, Xu Zhang, Yuting Jiang, Xinyue Li, Ying Xie, Zhiyu Ren, Zhimin Chen^*()

Key Laboratory of Functional Inorganic Material Chemistry (Ministry of Education), School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, Heilongjiang, China

Received:2026-01-26 Accepted:2026-03-11 Online:2026-11-18 Published:2026-09-09
Contact: *E-mail:zmchen@hlju.edu.cn(Z. Chen).
Supported by:
National Natural Science Foundation of China(22179035);Heilongjiang Provincial Natural Science Foundation Joint Fund Cultivation Project(PL2024B012);Fundamental Research Funds for the Universities of Heilongjiang Province of China(2023-KYYWF-1440)

摘要/Abstract

摘要：

氨(NH₃)是农业和制药领域不可或缺的原料, 同时也是一种极具潜力的无碳能源载体. 传统的Haber-Bosch工艺能耗高且碳排放量大, 因此, 通过可再生电能驱动的电催化硝酸盐还原反应(NitRR)成为实现温和条件下可持续合成NH₃的重要途径. 然而, 中性条件下的NitRR反应动力学缓慢, 且竞争性的析氢反应(HER)以及亚硝酸盐(NO₂^-)等副产物降低反应的选择性. 将NitRR中的串联步骤(即硝酸盐活化和后续加氢过程)分配到具有相应最佳活性的催化中心上, 是突破上述瓶颈的有效策略.

四氧化三钴(Co₃O₄)能促进水解离提供活性氢, 但其作为半导体导电性较差, 且对硝酸根(NO₃^-)的活化能力有限. 银(Ag)具备优异的导电性, 其d轨道电子结构与NO₃^-的最低未占分子轨道π轨道能级匹配, 可实现NO₃^-的高效活化. 然而, 仅靠简单的物理混合无法实现深度的功能协同, 长程的界面分离导致活性位点分离, 而界面处的能量失配则使关键中间体(如*NO₂)在迁移受阻, 过早脱附至电解液, 严重降低了反应的选择性. 为解决异质界面能量不匹配这一核心瓶颈, 本文通过预注入热熔合策略, 在Co₃O₄载体上成功构建了具有部分极化特征的Ag纳米团簇(PP-Ag/Co₃O₄). 实验结合密度泛函理论计算表明, 强烈的界面电子耦合作用稳定了界面处极化的Ag^δ⁺位点; 这些Ag^δ⁺位点具有适中的中间体吸附能, 在空间上紧邻Ag⁰和Co₃O₄位点, 从而构建了能量匹配的梯度吸附位点. 这种能量空间的连续性显著优化了反应中间体的迁移路径, 促进了NO₃^-在Ag位点上的活化与Co位点上的加氢过程之间的有效级联, 抑制中间体提前脱附. 得益于这种高效的催化级联, PP-Ag/Co₃O₄在中性条件下展现出卓越的电催化性能, 在-0.8 V vs. RHE的最佳电位下, 其NH₃法拉第效率高达96.2%, 生成速率达到12.3 mg h^-1 cm^-2, 显著优于单独的Ag和Co₃O₄催化剂. 该催化剂还表现出极高的工业应用潜力, 在0.1 A cm^-2的平均电流密度下可稳定运行132 h. 此外, 基于PP-Ag/Co₃O₄构建的可充电锌-硝酸根电池提供了5.42 mW cm^-2的出色峰值功率密度, 并具备超过100次的优异循环稳定性.

综上, 本工作采用预注入热熔合策略, 成功构建了PP-Ag/Co₃O₄, 形成了稳定的Ag-Ag^δ⁺/Co₃O₄异质界面. 强烈的界面电子耦合作用诱导产生梯度能量匹配, 从热力学层面实现了关键含氮中间体在串联反应步骤间的吸附能匹配. 这种连续的界面能量调节机制不仅显著提升了中性条件下硝酸盐还原产氨的催化效率和稳定性, 更为推动可持续氨电合成技术的发展提供了重要的理论参考价值.

关键词: 电催化硝酸盐还原, 能量匹配, 催化级联, 银/四氧化三钴异质界面, 锌-硝酸根电池

Abstract:

Although tandem-site multiphase catalysts have been explored for the electrochemical conversion of nitrate to ammonia (NH₃), achieving genuine phase synergy remains challenging due to energetic mismatches across the interface. Herein, a pre-infusing pyrolytic fusion strategy is developed to construct partially polarized Ag clusters on a Co₃O₄ support (PP-Ag/Co₃O₄). Strong interfacial electronic coupling stabilizes Ag^δ⁺ sites. These Ag^δ⁺ construct the relay sites with a gradient energy alignment feature, thereby facilitating a catalytic cascade enabling effective coupling between nitrate activation on Ag and subsequent hydrogenation on Co₃O₄. Experimental results demonstrate that PP-Ag/Co₃O₄ achieves a notable NH₃ Faradaic efficiency of 96.2%, a yield rate of 12.3 mg h^-1 cm^-2 under neutral conditions. Furthermore, the constructed Zn-NO₃^- battery based on PP-Ag/Co₃O₄ delivers an impressive power density of 5.42 mW cm^-2. This work highlights energy alignment engineering as an effective strategy for advancing efficient ammonia electrosynthesis.

Key words: Electrocatalytic nitrate reduction, Energy alignment, Catalytic cascades, Ag/Co₃O₄ heterointerface, Zn-NO₃^- battery

王智浩, 张宇昂, 张旭, 姜雨婷, 李欣悦, 谢颖, 任志宇, 陈志敏. 能量梯度匹配驱动催化级联实现协同硝酸盐电还原制氨[J]. 催化学报, 2026, 90: 287-297.

Zhihao Wang, Yuang Zhang, Xu Zhang, Yuting Jiang, Xinyue Li, Ying Xie, Zhiyu Ren, Zhimin Chen. Gradient energy alignment drives catalytic cascades for synergistic nitrate-to-ammonia electro-conversion[J]. Chinese Journal of Catalysis, 2026, 90: 287-297.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65150-9

https://www.cjcatal.com/CN/Y2026/V90/I11/287

图/表 5

Fig. 1. Structural characterizations of PP-Ag/Co3O4. (a) Schematic synthesis process. (b) HRTEM image. (c) FFT pattern and corresponding STEM-EDS elemental mapping. (d) XRD patterns of PP-Ag/Co3O4 and control samples.

Fig. 2. Electronic structure and interfacial coupling of PP-Ag/Co3O4. (a) High-resolution Ag 3d XPS spectra. (b) Co 2p XPS spectra. (c) O 1s XPS spectra. (d) Co K-edge XANES spectra. (e) FT k3-weighted EXAFS spectra. (f) WT contour plots.

Fig. 3. Electrocatalytic NitRR and Zn-NO3- battery performance of PP-Ag/Co3O4. (a) LSV curves. (b) Potential-dependent Faradaic efficiencies. NH3 Faradaic efficiencies (c) and yield rates (d). (e) Cycling stability. (f) Performance comparison with reported Ag/Co-based catalysts. (g) Polarization and power density curves of Zn-NO3- battery. (h) Galvanostatic discharge curves and NH3 yields. (i) Charge-discharge cycling stability.

Fig. 4. Mechanistic verification and in situ analyses of PP-Ag/Co3O4. Reaction potentials (a) and Tafel slopes (b) in different electrolytes. (c) In-situ ATR-SEIRAS spectra and local magnification revealing intermediate evolution. (d) In-situ EIS confirming accelerated charge and mass transfer.

Fig. 5. DFT investigation of energy alignment on PP-Ag/Co3O4. (a) Calculated *NO2 adsorption energies on Ag and Co sites. Free-energy diagrams for *NO2 desorption (b) and relay-mediated hydrogenation (c). (d) Differential and plane-averaged charge density. (e) PDOS of Ag, PP-Ag/Co3O4, and Co3O4. (f) Schematic illustration of *NO2 relay pathway on Ag-Agδ+/Co3O4 heterointerface.

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能量梯度匹配驱动催化级联实现协同硝酸盐电还原制氨

Gradient energy alignment drives catalytic cascades for synergistic nitrate-to-ammonia electro-conversion

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