光还原负载Ag优化Cu2O多面体电催化硝酸盐还原合成氨活性

doi:10.3976/j.issn.1002-4026.2025148

摘要/Abstract

摘要：

氨作为重要的化工原料,其传统合成工艺——哈伯-博施工艺存在高能耗、高排放等问题,因此开发绿色、高效的电催化合成氨技术具有重要意义。针对单一Cu₂O催化剂反应动力学迟滞以及电子转移速率较慢的问题,本文通过无模板化学沉淀法合成了26面体Cu₂O,并利用光还原法引入Ag颗粒负载于Cu₂O表面,降低催化剂阻抗,促进界面电荷传输,并增强了对*NO₂、*NH₂OH等反应中间体向NH₃转化的本征催化活性,抑制析氢反应和副产物生成,从而系统提升了电催化硝酸盐还原合成氨性能。电化学测试表明,Ag-Cu₂O在硝酸盐还原反应中表现出优异的催化性能,其氨法拉第效率最高达88%,优于Au-Cu₂O和纯Cu₂O,且副产物亚硝酸盐和竞争产物氢气生成量较少。该催化剂能够适应不同浓度${\mathrm{N}\mathrm{O}}_{3}^{-}$溶液,为宽浓度范围硝酸盐废水处理提供帮助。本研究为设计高性能、高稳定性的硝酸盐还原电催化剂提供了新思路,对推动电催化技术在废水处理和绿色合成氨领域的应用具有参考价值。

关键词: 电催化, 硝酸根还原制氨, 光还原, 银, 氧化亚铜

Abstract:

Ammonia is an essential chemical feedstock; however, its conventional synthesis via the Haber-Bosch process is associated with high energy consumption and substantial carbon emissions. Developing green and efficient electrocatalytic routes for ammonia synthesis is therefore of significant importance. To overcome sluggish reaction kinetics and limited electron transfer, 26-faceted Cu₂O polyhedra were synthesized using a template-free chemical precipitation method, followed by the deposition of Ag particles onto the Cu₂O surface via photoreduction. This catalyst design optimizes the electronic structure, facilitates interfacial charge transfer, and enhances the intrinsic activity for converting key reaction intermediates (such as *NO₂ and *NH₂OH) into NH₃. As a result, the hydrogen evolution reaction and by-product formation are suppressed, leading to improved electrocatalytic performance for nitrate reduction to ammonia. Electrochemical evaluations demonstrate that Ag-Cu₂O exhibits excellent catalytic activity for the nitrate reduction reaction, achieving a Faradaic efficiency of up to 88%, which outperforms Au-Cu₂O and pristine Cu₂O, while generating lower amounts of the nitrite by-product and the competing hydrogen product. The catalyst maintains effective performance across a wide range of nitrate concentrations, supporting its potential applicability in nitrate wastewater treatment with varying pollutant levels. This study provides new insights into the rational design of high-performance and durable electrocatalysts for nitrate reduction and offers a valuable reference for advancing electrocatalytic technologies in wastewater treatment and green ammonia synthesis.

Key words: electrocatalysis, nitrate reduction to ammonia, photoreduction, silver, copper oxide

中图分类号:

TQ113.247

程雅慧, 郭怡然, 温传敬. 光还原负载Ag优化Cu₂O多面体电催化硝酸盐还原合成氨活性[J]. 山东科学, 2026, 39(2): 50-61.

CHENG Yahui, GUO Yiran, WEN Chuanjing. Photoreduction-assisted Ag-loaded Cu₂O polyhedra for enhanced electrocatalytic nitrate reduction to ammonia[J]. Shandong Science, 2026, 39(2): 50-61.

图/表 12

图1

图2

图3

图4

图5

表1

图6

图7

图8

图9

图10

图11

参考文献 37

[1]	HUANG H, PERAMAIAH K, HUANG K W. Rethinking nitrate reduction: Redirecting electrochemical efforts from ammonia to nitrogen for realistic environmental impacts[J]. Energy & Environmental Science, 2024, 17(8): 2682-2685. DOI:10.1039/D4EE00222A.
[2]	JOSEPH SEKHAR S, SAMUEL M S, GLIVIN G, et al. Production and utilization of green ammonia for decarbonizing the energy sector with a discrete focus on Sustainable Development Goals and environmental impact and technical hurdles[J]. Fuel, 2024, 360: 130626. DOI:10.1016/j.fuel.2023.130626.
[3]	XIONG J, JIANG L Y, ZHU B T, et al. FeIr alloy optimizes the trade-off between nitrate reduction and active hydrogen generation for efficient electro-synthesis of ammonia in neutral media[J]. Advanced Functional Materials, 2025, 35(27): 2423705. DOI:10.1002/adfm.202423705.
[4]	JIAO F, XU B J. Electrochemical ammonia synthesis and ammonia fuel cells[J]. Advanced Materials, 2019, 31(31): 1805173. DOI:10.1002/adma.201805173.
[5]	LI J Y, XIONG Q C, MU X W, et al. Recent advances in ammonia synthesis: FromHaber-Bosch process to external field driven strategies[J]. ChemSusChem, 2024, 17(15): e202301775. DOI:10.1002/cssc.202301775.
[6]	ERFANI N, BAHARUDIN L, WATSON M. Recent advances and intensifications inHaber-Bosch ammonia synthesis process[J]. Chemical Engineering and Processing - Process Intensification, 2024, 204: 109962. DOI:10.1016/j.cep.2024.109962.
[7]	LIU Y, MA J W, HUANG S L, et al. Highly dispersed copper-iron nanoalloy enhanced electrocatalytic reduction coupled with plasma oxidation for ammonia synthesis from ubiquitous air and water[J]. Nano Energy, 2023, 117: 108840. DOI:10.1016/j.nanoen.2023.108840.
[8]	HUANG Y D, LIANG Y Q, JIANG H, et al. Enrichment of active hydrogen on nanoporous Ru/Co2P for enhanced electrocatalytic nitrate to ammonia[J]. Chemical Engineering Journal, 2025, 516: 164046. DOI:10.1016/j.cej.2025.164046.
[9]	CHEN G F, YUAN Y F, JIANG H F, et al. Electrochemical reduction of nitrate to ammoniavia direct eight-electron transfer using a copper-molecular solid catalyst[J]. Nature Energy, 2020, 5(8): 605-613. DOI:10.1038/s41560-020-0654-1.
[10]	MAENG J, JANG D, HA J, et al. Oxygen vacancy-controlled CuOx/N, Se Co-doped porous carbonvia plasma-treatment for enhanced electro-reduction of nitrate to green ammonia[J]. Small, 2024, 20(37): 2403253. DOI:10.1002/smll.202403253.
[11]	LI P P, LI R, LIU Y T, et al. Pulsed nitrate-to-ammonia electroreduction facilitated by tandem catalysis of nitrite intermediates[J]. Journal of the American Chemical Society, 2023, 145(11): 6471-6479. DOI:10.1021/jacs.3c00334. pmid: 36897656
[12]	QIU W X, CHEN X J, LIU Y T, et al. Confining intermediates within a catalytic nanoreactor facilitates nitrate-to-ammonia electrosynthesis[J]. Applied Catalysis B: Environmental, 2022, 315: 121548. DOI:10.1016/j.apcatb.2022.121548.
[13]	CHAO G J, ZONG W, ZHU J X, et al. Selective mass accumulation at the metal-polymer bridging interface for efficient nitrate electroreduction to ammonia and Zn-nitrate batteries[J]. Journal of the American Chemical Society, 2025, 147(25): 21432-21442. doi: 10.1021/jacs.5c00400 pmid: 40495693
[14]	ZONG W, GAO H Q, OUYANG Y, et al. Bio-inspired aerobic-hydrophobic Janus interface on partially carbonized iron heterostructure promotes bifunctional nitrogen fixation[J]. Angewandte Chemie International Edition, 2023, 62(27): e202218122. DOI:10.1002/anie.202218122.
[15]	YANG Y, SUN Y T, WANG Y N, et al. Self-triggering a locally alkaline microenvironment of Co₄Fe6 for highly efficient neutral ammonia electrosynthesis[J]. Journal of the American Chemical Society, 2025, 147(10): 8893-8905. doi: 10.1021/jacs.5c00688
[16]	LI Z Y, ZHENG M, YAN C S, et al. Stabilizing Cu0-Cuδ+ sitesvia ohmic contact interface engineering for ampere-level nitrate electroreduction to ammonia[J]. Nature Communications, 2025, 16: 8940. DOI:10.1038/s41467-025-63996-w.
[17]	ZHANG S, WU J H, ZHENG M T, et al. Fe/Cu diatomic catalysts for electrochemical nitrate reduction to ammonia[J]. Nature Communications, 2023, 14: 3634. DOI:10.1038/s41467-023-39366-9. pmid: 37337012
[18]	ZHANG B C, DAI Z C, CHEN Y X, et al. Defect-induced triple synergistic modulation in copper for superior electrochemical ammonia production across broad nitrate concentrations[J]. Nature Communications, 2024, 15: 2816. DOI:10.1038/s41467-024-47025-w. pmid: 38561364
[19]	TANG S S, XIE M H, YU S, et al. General synthesis of high-entropy single-atom nanocages for electrosynthesis of ammonia from nitrate[J]. Nature Communications, 2024, 15: 6932. DOI:10.1038/s41467-024-51112-3. pmid: 39138150
[20]	WEI J L, WANG J L, YU W Q, et al. Dualactivesite accelerated hydrogenation facilitates efficient electrochemical reduction of nitrate to ammonia[J]. Applied Catalysis B: Environment and Energy, 2025, 378: 125629. DOI:10.1016/j.apcatb.2025.125629.
[21]	BOUFELGHA S, AOUDIA K, HAMMACHE H, et al. Synergistic effect between Cu₂O electrodeposited thin film and carbon steel substrate on the electrocatalysis of nitrate reduction reaction[J]. Journal of the Indian Chemical Society, 2025, 102(8): 101820. DOI:10.1016/j.jics.2025.101820.
[22]	LIU Y, YAO X M, LIU X, et al. Cu²⁺1O/Ag heterostructure for boosting the electrocatalytic nitrate reduction to ammonia performance[J]. Inorganic Chemistry, 2023, 62(19): 7525-7532. doi: 10.1021/acs.inorgchem.3c00857
[23]	HAN M, GUO M H, YUN Y P, et al. Effect of heteroatom and charge reconstruction in atomically precise metal nanoclusters on electrochemical synthesis of ammonia[J]. Advanced Functional Materials, 2022, 32(29): 2202820. DOI:10.1002/adfm.202202820.
[24]	YAO Y Q, WANG Z F, SHEN H J, et al. Innovative interfacial hydrogen spillover in Ag-Cu₂O for selective electrohydrogenation of furfural[J]. International Journal of Hydrogen Energy, 2025, 158: 150523. DOI:10.1016/j.ijhydene.2025.150523.
[25]	FENG A L, HU Y D, YANG X X, et al. ZnO nanowire arrays decorated with Cu nanoparticles for high-efficiency nitrate to ammonia conversion[J]. ACS Catalysis, 2024, 14(8): 5911-5923. DOI:10.1021/acscatal.3c04398.
[26]	CHEN X, JIN W, ZHONG X Y, et al. Optimized kinetic pathways of active hydrogen generation at Cu₂O/Cu heterojunction interfaces to enhance nitrate electroreduction to ammonia[J]. Chinese Journal of Catalysis, 2025, 79: 78-90. DOI:10.1016/S1872-2067(25)64848-0.
[27]	WU K M, SUN C C, WANG Z N, et al. Surface reconstruction on uniform Cu nanodisks boosted electrochemical nitrate reduction to ammonia[J]. ACS Materials Letters, 2022, 4(4): 650-656. doi: 10.1021/acsmaterialslett.2c00149
[28]	HAI Y, LI X M, CAO Y, et al. Ammonia synthesis via electrocatalytic nitrate reduction using NiCoO2 nanoarrays on a copper foam[J]. ACS Applied Materials & Interfaces, 2024, 16(9): 11431-11439.
[29]	LI Y, GUO J Y, YANG Y W, et al. Atomically dispersed copper electrocatalysts with proton-feeding centers for efficient ammonia synthesis by nitrate electroreduction[J]. Advanced Functional Materials, 2025: e08619. DOI:10.1002/adfm.202508619.
[30]	DONG Y N, ZHAO C S, LI Y G, et al. Ammonia synthesis by nitrate reduction catalyzed by copper porphyrin metal-organic framework in tandem with cuprous oxide[J]. ACS Applied Energy Materials, 2025, 8(13): 9038-9048. doi: 10.1021/acsaem.5c00651
[31]	JANG D, MAENG J, KIM J, et al. Boosting electrocatalytic nitrate reduction reaction for ammonia synthesis by plasma-induced oxygen vacancies over MnCuOx[J]. Applied Surface Science, 2023, 610: 155521. DOI:10.1016/j.apsusc.2022.155521.
[32]	LIU H L, ZHANG S Y, PREMY T, et al. Pulsed electrocatalysis on iron-decorated copper foam enables efficient and selective ammonia synthesis from low-concentration nitrate[J]. Journal of Environmental Chemical Engineering, 2025, 13(5): 118539. DOI:10.1016/j.jece.2025.118539.
[33]	GUO C F, YANG S Y, WEI L T, et al. Modulation of the lattice structure of CuFe/copper foam catalysts by doping with Bi to improve the efficiency of electrocatalytic ammonia synthesis[J]. ACS Sustainable Chemistry & Engineering, 2025, 13(4): 1604-1616.
[34]	CHEN F S, ZHONG X Y, DING J J, et al. Trimesic acid modified copper-cobalt layered double hydroxide nanosheets boost electrocatalytic reduction of nitrate to ammonia[J]. Journal of Colloid and Interface Science, 2026, 701: 138664. DOI:10.1016/j.jcis.2025.138664.
[35]	WANG Q, SHEN Y. Electrocatalytic reduction of nitrate into ammonia by bimetallic copper-nickel catalysts[J]. Journal of Electroanalytical Chemistry, 2025, 987: 119110. DOI:10.1016/j.jelechem.2025.119110.
[36]	GUO X T, GAO R T, GAO Z H, et al. Grain boundary engineering on Cu-based electrocatalysts promotes nitrate reduction to ammonia production[J]. Journal of Energy Chemistry, 2025, 106: 351-359. DOI:10.1016/j.jechem.2025.01.036.
[37]	WANG Y Y, BAO T, CHEN L Y, et al. Boosting nitrate-to-ammonia conversion over copper-based electrocatalysts by facilitating hydrogenation and product desorption[J]. Angewandte Chemie (International Ed in English), 2025, 64(41): e202509090. DOI:10.1002/anie.202509090.

催化剂	电解液	FE/%	过电位(vs. RHE)/V	产率	引用
Ag-Cu₂O	0.1 mol/L Na₂SO₄ 50 mmol/L KNO₃	88	-0.9	568.66 μmol·h^-1 ·mg^-1	本文
Co_x-Cu₂O/Cu	0.1 mol/L Na₂SO₄ 500 mmol/L ${\mathrm{N}\mathrm{O}}_{3}^{-}$	86.2	-0.7	290.0 μmol·h^-1 ·mg^-1	[26]
Cu	0.1 mol/L KOH 10 mmol/L KNO₃	81.1	-0.5	2.16 mg·mg^-1·h^-1	[27]
NiCoO₂@Cu	0.1 mol/L Na₂SO₄ 0.1 mol/L NaNO₃	94.2	-0.7	5940.73 μg·h^-1·cm^-2	[28]
CuSA-NO/C	0.5 mol/L Na₂SO₄ 0.05 mol/L KNO₃	92.7	-0.2	24.9 mg·h^-1·mg^-1	[29]
Cu-TCPP/Cu₂O/CF	0.1 mol/L Na₂SO₄ 100 mg/L NO₃-N	90.22	-1	0.0937 mmol·h^-1·cm^-2	[30]
MnCuO_x	1 mol/L KOH 0.1 mol/L KNO₃	86.4	-0.63	9.4 mg·cm^-2·h^-1	[31]
Fe@CF	50 mmol/L Na₂SO₄ 20 mmol/L NaNO₃	99	150 min	93 μg·h^-1·cm^-2	[32]
Bi-CuFe/CF	1 mol/L KOH	46.8	-0.4	216.1 μg·h^-1·cm^-2	[33]
CuxCo_1-x-LDH/TA	0.1 mol/L Na₂SO₄ 0.01 mol/L ${\mathrm{N}\mathrm{O}}_{3}^{-}$	93.9	-0.6	355.9 μmol·mg^-1·h^-1	[34]
CuNi/CP	0.5 mol/L Na₂SO₄ 0.1 mol/L NaNO₃	90.36	-0.6	3.53 mg·h^-1·mg^-1	[35]
CuO/Ni₂O₃	32.3 mmol/L NaNO₃	~96	0.05	3.4 mmol·cm^-2·h^-1	[36]
Ca-Cu₂O-OA	0.5 mol/L Na₂SO₄ 0.1 mol/L NaNO₃	97.49	-0.9	15.02 mg·h^-1·cm^-2	[37]

光还原负载Ag优化Cu₂O多面体电催化硝酸盐还原合成氨活性

Photoreduction-assisted Ag-loaded Cu₂O polyhedra for enhanced electrocatalytic nitrate reduction to ammonia

RichHTML

PDF (PC)

赞

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 37

相关文章 15

Metrics

本文评价

推荐阅读 0

[1]	李万英, 王海燕, 汪慧铖, 张鹏, 方磊. 响应面法优化金银花中有机酸类成分提取工艺[J]. 山东科学, 2025, 38(4): 1-7.
[2]	潘翔宇, 靳钊, 关彤, 陈贝怡. 乙二胺-N-丙基改性硅胶的可控键合制备及其在银杏酸脱除中的应用研究[J]. 山东科学, 2024, 37(1): 51-58.
[3]	钱桂英, 钱云英, 吴晓明, 金凤珠. 超高效液相色谱-串联质谱结合化学计量学分析金银花中多组分含量[J]. 山东科学, 2023, 36(5): 1-8.
[4]	毕艳艳, 马庆文, 许辉, 刘健, 龙瑞, 唐伟铭, 郭田甜, 郝大伟. Box-Behnken Design响应面法优化银杏叶总黄酮柱层析纯化工艺[J]. 山东科学, 2022, 35(6): 8-15.
[5]	张会敏, 宋健, 徐林, 董学, 钟方晓. 经典名方银翘散薄层鉴别标准提升研究[J]. 山东科学, 2022, 35(4): 9-14.
[6]	唐志强,李小丽,许小涵,蒲高斌. 金银花U6启动子的克隆及转录活性分析[J]. 山东科学, 2022, 35(2): 11-17.
[7]	宁凡盛,路岩翔,曹桂云,孟兆青,闫慧娇,王岱杰. 银杏内酯C标准样品的研制[J]. 山东科学, 2022, 35(2): 18-28.
[8]	曹鑫磊, 姜浩, 杨宝山, 焦克芹, 王惠. 纳米银对小麦秸秆还田土壤中酶活性及微生物群落功能多样性的影响[J]. 山东科学, 2021, 34(3): 80-89.
[9]	丁晓彦, 林志军, 王岱. 金银花-连翘药对的成分和药理作用研究进展[J]. 山东科学, 2019, 32(3): 36-41.
[10]	刘倩，张敏敏，李圣波，梁琰，刘伟，程素盼，王晓，耿岩玲，赵恒强. HPLC-DAD法测定西藏产区金银花花蕾及叶中化学成分含量[J]. 山东科学, 2018, 31(4): 20-25.
[11]	张金成, 张永清, 梁从莲, 霍立群, 李佳. ICP-OES法测定市售金银花中8种金属元素含量[J]. 山东科学, 2017, 30(2): 20-24.
[12]	李文东, 高乾善,杨鹏,杨丙田,王晓. 银杏叶中银杏内酯提取工艺研究[J]. 山东科学, 2016, 29(5): 29-35.
[13]	李赛钰，徐清忠,王利红，栾玲玉，韩术鑫. 硝酸银分光光度法测定大气污染物中氯化氢[J]. 山东科学, 2014, 27(5): 85-87.
[14]	尹西翔，王利红,栾玲玉,刘静,韩术鑫,李赛钰. 金银花水浸泡液中的重金属含量分析及其人体健康风险评价[J]. J4, 2013, 26(6): 87-91.
[15]	王梅,刘峰,林昌虎，张清海，张永清，刘建华,王晓. 化学发光法检测不同干燥方法对金银花抗氧化活性和化学成分的影响[J]. J4, 2013, 26(2): 56-60.