蜂窝状AlCuZn的制备及其电催化CO2和NO3共还原产尿素研究

基金项目

有机废水污染深度处理新技术开发与应用(2024340603000314);安徽省学科(专业)带头人资助计划(DTR2025015);绿色和精准合成化学及应用教育部重点实验室自主(开放)课题(KLGPSCA202502)

中图分类号:

X78

文献标识码:

A

作者简介

成林玉(1999—),女,河南焦作人,硕士研究生,研究方向:环境与能源催化,E-mail:17739496045@163.com

通信作者

杨洋,副教授,E-mail:yangy@chnu.edu.cn

孟苏刚,教授,E-mail:sgmeng@chnu.edu.cn

流转信息

收稿日期 : 2025-10-01

修订日期 : 2026-01-30

引文格式

成林玉,刘欣,刘易,杨洋,张洁,鲁童宇,阚艳东,包先明,孟苏刚. 蜂窝状AlCuZn的制备及其电催化CO2和NO3共还原产尿素研究[J]. 铜业工程,2026(3):104-112.

Fabrication of Honeycomb-structured AlCuZn and the Application in Electrocatalytic Co-reduction of CO2 and NO3 for Urea Synthesis

Citations

Cheng Linyu,Liu Xin,Liu Yi,Yang Yang,Zhang Jie,Lu Tongyu,Kan Yandong,Bao Xianming,Meng Sugang. Fabrication of honeycomb-structured AlCuZn and the application in electrocatalytic co-reduction of CO2 and NO3 for urea synthesis [J]. Copper Engineering,2026(3):104-112.

铜业工程    第3期    104-112
doi10.3969/j.issn.1009-3842.2026.03.012
材料制备与加工工程(Material Preparation and Process Engineering)

蜂窝状AlCuZn的制备及其电催化CO2和NO3共还原产尿素研究

  • 成林玉 1,2
  • 刘欣 1,2
  • 刘易 1,2
  • 杨洋 1,2
  • 张洁 1,2
  • 鲁童宇 1,2
  • 阚艳东 1
  • 包先明 1,2
  • 孟苏刚 1
1.淮北师范大学 绿色和精准合成化学及应用教育部重点实验室安徽 淮北 235000
2.淮北师范大学 生命科学学院安徽 淮北 235000

作者简介

成林玉(1999—),女,河南焦作人,硕士研究生,研究方向:环境与能源催化,E-mail:17739496045@163.com

通信作者

杨洋,副教授,E-mail:yangy@chnu.edu.cn

孟苏刚,教授,E-mail:sgmeng@chnu.edu.cn

基金项目

有机废水污染深度处理新技术开发与应用(2024340603000314);安徽省学科(专业)带头人资助计划(DTR2025015);绿色和精准合成化学及应用教育部重点实验室自主(开放)课题(KLGPSCA202502)

中图分类号:

X78

文献标识码:

A

流转信息

收稿日期 : 2025-10-01     修订日期 : 2026-01-30     

引文格式

成林玉,刘欣,刘易,杨洋,张洁,鲁童宇,阚艳东,包先明,孟苏刚. 蜂窝状AlCuZn的制备及其电催化CO2和NO3共还原产尿素研究[J]. 铜业工程,2026(3):104-112.

摘要

在全球碳中和趋势下,开发高效低能耗的尿素合成技术具有重要意义。电催化技术可以在常温常压下直接将CO2和硝酸盐(NO3)共还原合成尿素,是一种极具前景的策略,受到研究者广泛关注。然而,当前催化体系存在传质效率低、催化剂活性不足、稳定性差等问题,开发高效电催化剂依然面临巨大挑战。本研究通过简单的碱刻蚀方法,成功制备出蜂窝状多孔结构的AlCuZn合金催化剂。在设计环境条件下,AlCuZn-0.5催化剂在–0.3 V(vs. RHE)时尿素法拉第效率高达65.7%,是原始AlCuZn的1.4倍;产率为152.4 μg/(h·mgcat),是AlCuZn的1.8倍。循环试验和反应前后的X射线衍射(XRD)结果表明,改性后的AlCuZn具有良好的性能稳定性与结构稳定性。刻蚀后的AlCuZn-0.5和Al-Cu-Zn之间具有更好的协同效应,有利于C-N偶联反应的发生,提高了尿素的选择性;多孔结构提高了反应物的传质效率,降低了电荷转移阻力,同时也能暴露更多活性位点,有效提高尿素的生成速率。本研究制备的AlCuZn-0.5在尿素电催化合成中具有广泛应用前景,为高效电催化NO3和CO2的C-N耦合提供了新的设计思路。

关键词

AlCuZn催化剂;电催化;尿素合成;C-N偶联;选择性;

Fabrication of Honeycomb-structured AlCuZn and the Application in Electrocatalytic Co-reduction of CO2 and NO3 for Urea Synthesis

  • Cheng Linyu 1,2
  • Liu Xin 1,2
  • Liu Yi 1,2
  • Yang Yang 1,2
  • Zhang Jie 1,2
  • Lu Tongyu 1,2
  • Kan Yandong 1
  • Bao Xianming 1,2
  • Meng Sugang 1
1.Key Laboratory of Green and Precise Synthetic Chemistry and ApplicationsMinistry of EducationHuaibei normal universityHuaibei 235000China
2.School of Life SciencesHuaibei normal universityHuaibei 235000China

Citations

Cheng Linyu,Liu Xin,Liu Yi,Yang Yang,Zhang Jie,Lu Tongyu,Kan Yandong,Bao Xianming,Meng Sugang. Fabrication of honeycomb-structured AlCuZn and the application in electrocatalytic co-reduction of CO2 and NO3 for urea synthesis [J]. Copper Engineering,2026(3):104-112.

Abstract

Under the global carbon neutrality initiative, the advancement of efficient and low-energy urea synthesis technologies holds crucial importance for sustainable development in agriculture and industry. Electrocatalytic technology enables direct co-reduction of CO2 and NO3 for urea synthesis under ambient conditions, emerging as a highly promising strategy that has garnered significant research interest. Nevertheless, current electrocatalytic systems are constrained by low mass transfer efficiency, insufficient catalytic activity, and poor stability, posing substantial challenges for developing high-performance electrocatalysts. In this study, a honeycomb-like porous AlCuZn alloy catalyst was successfully fabricated through a facile alkali etching approach. At ambient conditions, the optimized AlCuZn-0.5 catalyst demonstrated a remarkable urea Faradaic efficiency of 65.7% at –0.3 V (vs. RHE), representing 1.4-fold enhancement over pristine AlCuZn, with a corresponding yield of 152.4 μg/(h·mgcat) achieving 1.8-fold improvement. Electrochemical cycling tests and pre-/post-reaction X-ray diffraction (XRD) analyses confirmed catalyst's superior operational stability and structural integrity. The etched AlCuZn-0.5 manifests enhanced synergistic effects among Al-Cu-Zn components, which facilitated C-N coupling reactions and improved urea selectivity. Porous architecture of the material not only enhanced reactant mass transfer but also reduced charge transfer resistance while exposing abundant active sites, collectively boosting urea production rate. This work established a novel design paradigm of C-N coupling for efficient electrocatalysis of NO3 and CO2, positioning AlCuZn-0.5 as a prospective catalyst for sustainable urea synthesis.

Keywords

AlCuZn catalyst;electrocatalysis;urea synthesis;C-N coupling;selectivity;



二氧化碳(CO2)是导致温室效应的主要气体之一,硝酸盐(NO3)是工业废水中的主要污染物,两者均对环境和人类健康构成潜在威胁  Mostafaeipour A,Bidokhti A,Fakhrzad M B,et al. A new model for the use of renewable electricity to reduce carbon dioxide emissions [J]. Energy,2022,238:121602.
 Garcia-Segura S,Lanzarini-Lopes M,Hristovski K,et al. Electrocatalytic reduction of nitrate:Fundamentals to full-scale water treatment applications [J]. Applied Catalysis B:Environmental,2018,236:546-568.
1-2
。尿素作为重要的有机肥料之一,对全球农业发展具有关键作用  Cui Z J,Wang H H,Li C L,et al. Three birds with one stone:Electrocatalytic C-N coupling for carbon neutrality,nitrogen resource utilization,and urea synthesis [J]. Renewable and Sustainable Energy Reviews,2024,205:114822.
3
。现有的尿素生产方法需要在苛刻的高温高压环境下进行,消耗大量的化石燃料  陈红梅,杨泽群,陈搏实,等. CO2与NO-2/NO-3电催化合成尿素研究进展 [J]. 能源环境保护,2023,37(3):88-97.
4
。因此,开发一种能够在温和条件下生产尿素的绿色技术迫在眉睫。将CO2和NO3通过电催化反应合成尿素是一种可持续且环境友好的技术  Zhang C,Chen S J,Guo L W,et al. Recent advances in urea electrocatalysis:applications,materials and mechanisms [J]. Chinese Journal of Chemistry,2024,42(24):3441-3468.
5
,该方法对实现CO2固定和工业废水中NO3污染物的资源化利用具有重要意义。此外,该策略还可有效降低传统尿素生产的能源消耗,促进实现可持续发展的目标。

铜基材料对二氧化碳还原反应(CO2RR)具有显著的催化活性,可将CO2深度还原为多碳产物  Huang M F,Wang C J,Yuan Y R,et al. Doping engineering in copper-based electrocatalysts:a strategic approach for enhancing CO2 electroreduction efficiency [J]. Journal of Energy Chemistry,2026,113:622-668.
 Li Y,Sun Y,Yu M. Strategies for improving product selectivity in electrocatalytic carbon dioxide reduction using copper-based catalysts [J]. Advanced Functional Materials,2024,34(51):2410186.
 Wang Y H,Liu J L,Zheng G F. Designing copper-based catalysts for efficient carbon dioxide electroreduction [J]. Advanced Materials,2021,33(46):2005798.
6-8
。Zheng等  Zeng J Q,Castellino M,Fontana M,et al. Electrochemical reduction of CO2 with good efficiency on a nanostructured Cu-Al catalyst [J]. Frontiers in Chemistry,2022,10:931767.
9
通过调节Cu/Al比优化了Cu-Al催化剂,该催化剂在KHCO3电解液中对甲酸(HCOOH)有良好的选择性,在KOH电解液中则提高了乙烯(C2H4)的选择性。Zn基催化剂能将NO3高效还原至NH3,并能抑制副反应(如析氢反应)  Singh B,Draksharapu A. Zinc-based materials for electrocatalytic reduction reactions:progress and prospects [J]. Materials Chemistry Frontiers,2025,9(15):2287-2321.
10
。Wu等  Wu L M,Feng J Q,Zhang L B,et al. Boosting electrocatalytic nitrate-to-ammonia via tuning of N-intermediate adsorption on a Zn-Cu catalyst [J]. Angewandte Chemie International Edition,2023,62(43):e202307952.
11
合成了Zn掺杂Cu催化剂并用于电催化硝酸盐还原,发现Zn掺杂在调节中间体吸附强度、增强亚硝酸盐转化、改变吸附*NO物种的构型以及降低反应能垒方面具有关键作用,有利于NO3高效转化为NH3。此外,研究表明,二元或者多元金属的协同作用,可促进电催化C-N偶联反应的进行,提高尿素选择性。Deng等  Deng T,Jia S Q,Xue C,et al. Phosphorus-doped Cu/Fe2O3 electrocatalysts with optimized synergy between the different sites for efficient urea electrosynthesis [J]. Journal of the American Chemical Society,2025,147(36):32924-32931.
12
研制了一种磷掺杂的Cu/Fe2O3催化剂(P-Cu/Fe2O3),该催化剂具有优异的尿素电合成性能。Zhou等  Zhou Y B,Wang M F,Zhang L F,et al. Quaternary medium-entropy alloy metallene with strong charge polarization for highly selective urea electrosynthesis from carbon dioxide and nitrate [J]. ACS Nano,2025,19(7):7273-7282.
13
设计了四元PdCuCoZn中熵合金,用于高选择性电合成尿素,效果良好。因此,合理设计多元协同催化剂,是实现高选择性和高活性尿素电合成的有效策略。

AlCuZn合金因价格低廉、易制备以及独特的还原性等优势而被广泛应用。例如:Ren等  Ren D Z,Wan X Y,Jin F M,et al. Selective hydrogenation of levulinate esters to 1,4-pentanediol using a ternary skeletal CuAlZn catalyst [J]. Green Chemistry,2016,18(22):5999-6003.
14
制备了一种高效的非贵金属骨架CuAlZn催化剂,以生物基乙酰丙酸酯为原料合成1,4-戊二醇(1,4-POD);Zhao等  Zhao L,Liu Q X,Wu H,et al. Facile depolymerization of lignin into phenolics via self-hydrogen transfer hydrogenolysis over a skeletal CuZnAl catalyst [J]. Green Chemistry,2025,27(21):6232-6243.
15
运用骨架状CuZnAl催化剂,将木质素高效解聚成酚类物质;Vu等  Vu V N,Pham T H T,Chanthavong M,et al. Enhanced photocatalytic degradation of rhodamine-B under led light using CuZnAl hydrotalcite synthesized by co-precipitation technique [J]. Inorganics,2022,10(7):89.
16
采用共沉淀法合成CuZnAl水滑石,增强了LED光催化降解罗丹明B的性能。AlCuZn合金在电催化CO2和NO3共还原产尿素领域鲜有报道,有待深入研究。鉴于AlCuZn合金中Al和Zn可与强碱发生反应,释放出氢气,因此可利用碱刻蚀法制备多孔AlCuZn合金,并调控Al、Cu、Zn三种元素的比例。通过多金属协同效应有望实现CO2和NO3还原过程中C-N偶联的高效进行,进而促进尿素的生成。

基于上述分析,本研究采用NaOH碱液对商业AlCuZn合金进行刻蚀,得到了蜂窝状结构的AlCuZn合金催化剂,并将其用于电催化NO3和CO2共还原合成尿素。该催化剂在–0.3 V(vs. RHE)条件下的尿素法拉第效率达到65.7%,尿素产率为152.4 μg/(h·mgcat),具有良好的循环稳定性。实验表明,多种金属之间的协同效应能够同时强化CO2和NO3的吸附和活化,并通过稳定关键中间体来降低C-N偶联的能垒。本研究不仅为尿素合成提供了一种环境友好的新路径,也为设计用于复杂多分子耦合反应的高效电催化剂提供了新的见解。

1     实验

1.1     试剂

AlCuZn合金(纯度为99.0%)购于上海阿达玛斯试剂有限公司。氢氧化钠(NaOH,纯度≥96.0%)、无水乙醇(C2H5OH,纯度≥99.7%)、硝酸钾(KNO3,纯度≥99.0%)、碳酸氢钾(KHCO3,纯度≥99.5%)、硫酸(H2SO4,质量分数为95%~98%)、浓磷酸(H3PO4,质量分数为85%)、异丙醇(C3H8O,质量分数为≥99.7%)、二乙酰一肟(C4H7NO2,纯度为98%)、氨基硫脲(CH5N3S,纯度为98%)、三氯化铁六水合物(FeCl3·6H2O,纯度≥99.0%)等试剂均购自国药集团化学试剂有限公司。这些试剂为分析纯级,未进一步纯化。

1.2     催化剂的制备

首先,将AlCuZn合金研磨成75~150 μm的颗粒。制备质量分数为20%的NaOH(6 g NaOH溶解在50 mL去离子水中),置于冰水浴中使温度维持在0~5 ℃。随后将AlCuZn合金缓慢加入碱液中。达到预定刻蚀时间后,将粉末过滤,并用去离子水反复洗涤直至滤液呈中性。最后,将粉末在真空干燥箱中烘干,得到所需催化剂样品。将催化剂命名为AlCuZn-xx=0.5、3.5),其中x表示刻蚀时间(单位:h)。NaOH刻蚀AlCuZn合金的反应方程式如下:

Al+H2O+NaOH→Na[Al(OH)4]+H2
式(1)

Zn+H2O+NaOH→Na[Zn(OH)4]+H2
式(2)

1.3     表征方法

晶体结构采用Cu Kα X射线衍射仪(XRD,Bruker D8 Advance,λ=0.1540 nm)进行测定,仪器操作电压和电流分别为40 kV和40 mA,扫描速度为3 (°)/min。采用配备能谱仪的扫描电子显微镜(Regulus 8220)对催化剂的形貌和微观结构进行分析。

1.4     电化学性能测试

使用电化学工作站(CS310M,武汉科思特仪器股份有限公司)以及由Nafion膜隔开的H型电解池进行电化学测量。工作电极制备方法如下:将10 mg催化剂与500 μL异丙醇和20 μL 5%的Nafion溶液混合,超声处理1 h使催化剂混合均匀。随后,将50 μL的催化剂均匀滴涂到1 cm×1 cm的碳纸上,并在烘箱中以60 ℃干燥过夜。1 cm×1 cm碳纸电极作为工作电极,Ag/AgCl(饱和KCl)电极作为参比电极,1 cm×1 cm铂片电极作为对电极。由于HCO3/CO32−缓冲对能有效维持稳定的近中性pH环境,这对于抑制析氢反应、促进硝酸盐还原至关重要  Shang S Y,Duan W C,Zeng X,et al. Boosted nitrate and CO2 reduction for urea electrosynthesis on p-block Bi dispersed Ru alloys [J]. ACS Sustainable Chemistry & Engineering,2025,13(7):2906-2912.
 Du W Y,Sun Z Y,Shang S Y,et al. Boosting electroreduction of nitrate and CO2 to urea on a tandem Fe1/MoS2 catalyst [J]. ACS Nano,2024,18(40):27718-27726.
 Zhao C,Jin Y,Yuan J K,et al. Tailoring activation intermediates of CO2 initiates C-N coupling for highly selective urea electrosynthesis [J]. Journal of the American Chemical Society,2025,147(10):8871-8880.
17-19
。因此,在电化学性能测量之前,将CO2气体(99.999%)通入50 mL含0.1 mol KNO3和0.1 mol KHCO3电解质溶液,以除去空气并使溶液中的CO2达到饱和。线性扫描伏安法(LSV)在–1.5~0 V电位下,以10 mV/s扫描速率进行测试。重复扫描过程,直至得到的曲线达到稳定状态。随后,在非法拉第区域进行循环伏安(CV)测试,分别以20、40、60、80、100、120 mV/s扫描速率循环扫描10圈,以确定电化学活性表面积,计算得到双电层电容值(Cdl)。电化学阻抗(EIS)测试在0.01 Hz ~ 100 kHz内施加10 mV的交流电压进行  陈嘉磊,廖雪龙,陈山,等. 三维自支撑的铜铋双金属电沉积制备及其电催化还原CO2性能研究 [J]. 铜业工程,2023(1):1-11.
20

1.5     产物检测

通过法拉第效率来量化表征电催化测试产物的转化效率。其中,目标产物尿素的检测按二乙酰一肟显色法,用紫外-可见分光光度仪测定。

显色剂配置。溶液A:将10 mL浓磷酸,30 mL浓硫酸和60 mL去离子水混合均匀后,再加入10 mg三氯化铁超声混合均匀。溶液B:将0.5 g二乙酰一肟和10 mg氨基硫脲溶解在100 mL纯水中超声溶解。具体步骤如下:将含尿素溶液与溶液A、溶液B以1∶2∶1(尿素∶A∶B=1∶2∶1)的比例混合,然后在100 ℃水浴锅中加热30 min,冷却至室温,在525 nm波长处测吸光度。

根据紫外-可见分光光度仪测得的结果,按式(3)计算反应后液体中尿素的法拉第效率。

FE=16×F×c×V60.06×Q×100%
式(3)

式中:FE是尿素的法拉第效率,%;F是法拉第常数,为96485 C/mol;c是测得的尿素浓度,g/L;V是电解时阴极池的液体体积,L;Q是反应过程中转移的电荷总量,C。

尿素产率可通过式(4)计算。

Yurea=curea×Vt×m
式(4)

式中:Yurea为尿素产率,μg/(h·mgcat);curea表示尿素的测量浓度,μg/mL;V为阴极室电解液总体积,为50 mL;t为电催化的反应时间,为1 h;m为催化剂负载量,为0.96 mg。

2     结果与讨论

2.1     结构表征与物相分析

为了了解催化剂的化学组成,对AlCuZn合金催化剂进行了XRD表征。如图1所示,AlCuZn合金主要由Al2Cu(PDF # 89-1981)和Al(OH)3(PDF # 70-2038)组成。其中位于29.4°、37.9°、42.1°、42.7°、47.4°、47.9°的衍射峰分别对应于Al2Cu的(200),(211)、(220)、(112)、(310)、(202)晶面;位于44.2°的衍射峰则对应于Al(OH)3的(204)晶面。没有刻蚀的AlCuZn合金呈现出多个尖锐的衍射峰,这归因于Al2Cu合金相。经过刻蚀处理后,对应于Al(OH)3(204)晶面的衍射峰强度逐渐增强,这是由于在碱刻蚀之后,金属Al与碱性溶液反应生成了含铝氢氧化物。且随着刻蚀时间的延长,Al2Cu位于29.4°、37.9°和42.7°处的衍射峰强度逐渐减弱,这说明归属于Al2Cu的(200)、(211)和(112)晶面被逐渐刻蚀。但位于Al(OH)344.2°处的衍射峰强度逐渐增强,这说明随着碱刻蚀时间的增长,Al(OH)3的(204)面逐渐暴露。有研究表明,碱刻蚀后AlCuZn合金空隙中的Al可产生晶格缺陷,从而提高催化剂的活性。但是碱刻蚀时间过长,导致骨架合金中的Al含量过低,使得催化剂不能保持很高的活性  Jiang N M,Sun H,Ren D Z,et al. A structure-activity controllable synthesis of skeletal CuAlZn catalyst for hydrogenation of bicarbonate to formic acid in water [J]. Journal of CO2 Utilization,2017,20:218-223.
21
。且随着Al和Zn的逐渐刻蚀,暴露出更多Cu位点,使得电催化产尿素中CO2RR反应得到增强  Li B,Guo H J,Xiong Z,et al. The solvent-free hydrogenation of butyl levulinate to γ-valerolactone and 1,4-pentanediol over skeletal Cu-Al-Zn catalyst [J]. Molecular Catalysis,2023,540:113046.
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图1     AlCuZn合金的XRD图谱
Fig. 1     XRD patterns of AlCuZn alloys

通过扫描电子显微镜(SEM)来表征催化剂的形貌特征  吴承扬,张玉,肖卫平. PtNi/MXene纳米复合材料的设计合成及其氧还原性能研究 [J]. 稀有金属,2023,47(12):1747-1755.
 马晓晶,赵明珠,郭成英,等. 硫钒共掺杂三氧化二铁纳米颗粒的制备及其电催化氮气还原性能研究 [J]. 聊城大学学报(自然科学版),2021,34(1):62-69.
 Huang Y B,Zhang J L,Zhang X,et al. Catalytic depolymerization of lignin via transfer hydrogenation strategy over skeletal CuZnAl catalyst [J]. Fuel Processing Technology,2022,237:107448.
23-25
。从图2中可以看出,未刻蚀的AlCuZn合金在SEM中呈现出光滑的表面。经过刻蚀处理后,催化剂的孔隙结构逐渐增多,表明Al和Zn与NaOH反应后逐渐被刻蚀。随着刻蚀时间的延长,催化剂表面粗糙度逐渐增加并形成丰富的孔隙结构,有利于催化性能的提升  马晓晶,赵明珠,郭成英,等. 硫钒共掺杂三氧化二铁纳米颗粒的制备及其电催化氮气还原性能研究 [J]. 聊城大学学报(自然科学版),2021,34(1):62-69.
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。由能量色散X射线谱(EDS)可以看出,Cu、Zn和Al元素都呈现均匀分散状态,O元素可能来自金属氧化物  Huang Y B,Zhang J L,Zhang X,et al. Catalytic depolymerization of lignin via transfer hydrogenation strategy over skeletal CuZnAl catalyst [J]. Fuel Processing Technology,2022,237:107448.
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。由表1可知,当刻蚀0.5 h时,Cu的质量分数有所上升,之后随着刻蚀时间的增加而减小,而Al的质量分数是先增加后下降;Zn和O的质量分数随着刻蚀时间的延长逐渐增加,这可能是刻蚀时一部分金属被氧化所致。这表明AlCuZn-0.5有最多的Cu位点,可高效催化CO2还原生成*CO中间体,进而提升C-N偶联合成尿素的效率。

图2     (a) AlCuZn,(b) AlCuZn-0.5和(c) AlCuZn-3.5的SEM图像;(d) AlCuZn-0.5的EDS元素分布图
Fig. 2     SEM images of (a) AlCuZn,(b) AlCuZn-0.5 and (c) AlCuZn-3.5 alloys;(d) EDS mapping of AlCuZn-0.5 alloy
表1     催化剂的元素组成
Table 1     Elemental analysis of catalysts (%,mass fraction)
Electrodes Al Cu Zn O
AlCuZn 43.29 52.71 1.39 2.61
AlCuZn-0.5 24.46 53.31 2.27 19.96
AlCuZn-3.5 31.17 26.9 6.83 35.1

2.2     电化学性能研究

在室温条件下,采用封闭H型电解池对催化剂的电催化CO2和NO3共还原合成尿素性能进行了评估。图3(a)对比了3种样品在CO2饱和气氛下的LSV曲线  Liu J F,Zhang S B,Mao Z X,et al. Optimizing the electronic structure of copper and cobalt dual sites for efficient electrosynthesis of urea [J]. Inorganic Chemistry Frontiers,2025,12(9):3426-3437.
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,AlCuZn-0.5的电流密度更高,表明碱刻蚀的AlCuZn合金在尿素电合成中可诱导NO3和CO2快速电催化共还原。图3(b)中对比了3种反应条件下的LSV图,电流密度遵循以下顺序:I(KNO3)<I(KNO3+KHCO3+CO2)<I(KHCO3+CO2)。结果表明,CO2和NO3共同还原形成C–N键产生的电流密度介于独立的NO3RR和CO2RR之间。这表明,在共电解过程中,竞争性析氢反应(HER)和NO3RR被有效抑制,而CO2RR显著增强。

图3     (a) 催化剂在CO2饱和的0.1 mol KHCO3+KNO3溶液中的LSV图;(b) 对比3种不同条件下的LSV图
Fig. 3     (a) LSV curves of catalysts in CO2-saturated 0.1 mol KHCO3 and KNO3 solution;(b) Comparison of LSV curves under different conditions

3种催化剂在不同电压下催化转化CO2和NO3合成尿素的性能如图4(a~c)所示,i-t曲线如图4(d~f)所示。由图4(a)可知,原始AlCuZn合金催化剂尿素法拉第效率和尿素产率随着电位的增加,呈现上升的趋势。由图4(b)可见,在AlCuZn-0.5合金催化剂中,尿素产率和法拉第效率呈现先增高后下降的趋势,且在–0.3 V(vs. RHE)时尿素产率和法拉第效率达到最高,分别为152.4 μg/(h·mgcat)和65.7%。从图4(c)可以看出,AlCuZn-3.5催化剂呈现出与AlCuZn-0.5一样的趋势,在–0.3 V(vs. RHE)时尿素法拉第效率为48.4%,尿素产率为143.8 μg/(h·mgcat)。由此可知,AlCuZn合金碱刻蚀0.5 h时尿素产率和法拉第效率最高,且随着刻蚀时间的延长呈现下降趋势。这表明刻蚀0.5 h时催化剂中Al,Cu,Zn比例达到最佳,使得Zn主导的NO3还原(*NH2)与Cu主导的CO2还原(*CO)串联进行,最终在Cu-Zn界面完成C-N偶联(*CO+*NH2 →*CONH2 → 尿素)。Al通过电子调控减少限速步骤(如*COOH形成或C-N偶联)的能垒,提升整体效率。这种三元金属之间的协同效应,使电催化尿素合成具有高选择性以及高效率  Luo Y T,Xie K,Ou P F,et al. Selective electrochemical synthesis of urea from nitrate and CO2via relay catalysis on hybrid catalysts [J]. Nature Catalysis,2023,6(10):939-948.
 Zhang H,Liu J J,Xu Z H,et al. Tailoring Cu-based nanoalloys for highly selective electrochemical urea synthesis from CO2 and nitrate [J]. ACS Catalysis,2025,15(11):8966-8978.
 Zhang Y,Li Z H,Chen K,et al. Promoting electroreduction of CO2 and NO3– to urea via tandem catalysis of Zn single atoms and In2O3-x [J]. Advanced Energy Materials,2024,14(47):2402309.
27-29

图4     (a) AlCuZn,(b) AlCuZn-0.5和 (c) AlCuZn-3.5催化剂上尿素的法拉第效率和产率;(d) AlCuZn,(e) AlCuZn-0.5和 (f) AlCuZn-3.5催化剂反应时的电流-时间曲线
Fig. 4     Faradaic efficiency of urea production and urea yield rate on (a) AlCuZn,(b) AlCuZn-0.5 and (c) AlCuZn-3.5 catalysts;I-t curves of the (d) AlCuZn,(e) AlCuZn-0.5 and (f) AlCuZn-3.5 catalysts during the reaction

催化剂的稳定性是评价催化剂性能的另一个重要指标  王宇婷. 钴基纳米材料的制备及其电解水催化性能的应用 [D]. 绵阳:西南科技大学,2021.
30
。如图5(a,b)所示,在4次连续循环实验中,尿素的法拉第效率总体保持稳定。通过XRD可以看出,除负载碳纸的碳峰外,反应前后AlCuZn-0.5催化剂的特征峰基本保持不变,表明AlCuZn-0.5催化剂具有良好的循环稳定性以及结构稳定性。如图5(c)所示,与各种报道的合金催化剂相比,AlCuZn催化剂表现出优异的电化学尿素合成性能  Shang S Y,Duan W C,Zeng X,et al. Boosted nitrate and CO2 reduction for urea electrosynthesis on p-block Bi dispersed Ru alloys [J]. ACS Sustainable Chemistry & Engineering,2025,13(7):2906-2912.
17
 Li K,Li Z B,Guo J,et al. Electrocatalytic synthesis of urea from carbon dioxide and nitrate over ZnO-based supported palladium-copper alloy catalysts [J]. Industrial & Engineering Chemistry Research,2025,64(30):14841-14849.
 Zhang Q Q,Li R Y,Li Z J,et al. Mild and scalable synthesis of a high performance CrFeCoNiRu0.05 high entropy nano-alloy/carbon electrocatalyst for efficient urea production with a chelate-based ionic liquid [J]. New Journal of Chemistry,2024,48(21):9738-9747.
 Yu X,Zeng S Q,Li R,et al. Tandem catalysis of CuCo alloy@N-doped hollow carbon spheres boosting urea electrosynthesis from nitrate and CO2 [J]. Chemical Engineering Journal,2025,519:165559.
 Sun Z S,Xiang X Y,Zhao Q P,et al. Efficient electrocatalytic urea synthesis from CO2 and nitrate over the scale-up produced FeNi alloy-decorated nanoporous carbon [J]. Chinese Journal of Catalysis,2024,65:153-162.
 Zhang Q Q,Li R Y,Li Z J,et al. Improvement of electrocatalytic performance in MnFeCoNiCu2 high-entropy alloy for urea synthesis by introducing functional graphene quantum dot and copper-rich phase [J]. Journal of Alloys and Compounds,2025,1015:178833.
 Wu T T,Tian Z H,Zhang Z Y,et al. Electrocatalytic urea synthesis from NO and CO2 on In1Pd single atom alloys [J]. Dalton Transactions,2025,54(39):14710-14715.
 Wan Y Y,Zhang Z Y,Qian J M,et al. Single-atom Rh1 alloyed co for urea electrosynthesis from CO2 and NO3– [J]. Nano Letters,2024,24(35):10928-10935.
 Wang F Z,Shang S Y,Li Z H,et al. Selective urea electrosynthesis from nitrate and CO2 on isolated copper alloyed ruthenium [J]. ACS Energy Letters,2024,9(9):4624-4632.
 Feng P Y,Ke B Q,Wang S,et al. Atomic-scale Mott-Schottky analogy in SnCu nanoalloy promote high-efficiency urea electrosynthesis at ultralow potential [J]. Angewandte Chemie International Edition,2025,64(36):e202509834.
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图5     (a) 4次循环实验中AlCuZn-0.5的尿素法拉第效率图;(b) 反应前后AlCuZn-0.5的XRD对比图;(c) 对各种催化剂的性能进行比较
Fig. 5     (a) Faradaic efficiency for urea production of AlCuZn-0.5 during four consecutive cycling tests;(b) XRD patterns of AlCuZn-0.5 before and after reaction;(c) Comparison of the performance among different catalysts

为了进一步探究碱刻蚀对CO2和NO3在AlCuZn合金催化剂上的反应动力学,分别通过CV、ECSA、EIS测量,系统地评估催化剂在C-N偶联反应中的电催化性能(图6)。采用不同扫描速率进行循环伏安(CV)测试,通过计算不同催化剂的双电层电容(Cdl)来评估催化剂的电化学活性表面积(ECSA)  Yang Y D,Wu G Z,Jiang J D,et al. Stabilization of Cuδ+ sites within MnO2 for superior urea electro-synthesis [J]. Advanced Materials,2024,36(41):2409697.
 孙梦龙,党姣娥,张永伟,等. ZIF-8/ZIF-67衍生钴氮共修饰碳的合成及电催化性能研究 [J]. 稀有金属,2024,48(2):288-295.
40-41
。如图6(d)所示,AlCuZn、AlCuZn-0.5、AlCuZn-3.5催化剂的双电层电容值(Cdl)分别为0.236、0.5、0.273 mF/cm2,其中,AlCuZn-0.5表现出最高的双电层电容值。这一差异表明,AlCuZn-0.5催化剂具有更多暴露的活性位点,有利于CO2和NO3的吸附和活化,促进C-N偶联合成尿素。采用电化学阻抗谱(EIS)研究电催化过程中催化剂界面处的电子/离子传输动力学  Zhang H,Liu J J,Xu Z H,et al. Tailoring Cu-based nanoalloys for highly selective electrochemical urea synthesis from CO2 and nitrate [J]. ACS Catalysis,2025,15(11):8966-8978.
28
 廖凡,陈子亮,康振辉. 主族元素在过渡金属基电解水催化剂中的应用研究进展 [J]. 稀有金属,2023,47(1):1-27.
42
。如图6(e)所示,多孔结构的AlCuZn-0.5催化剂表现出最小的电荷转移电阻,表明CO2和NO3在其电解质/多孔催化剂界面处具有更高的传质速率和更小的传输阻力。这一结果表明,AlCuZn-0.5催化剂在电催化过程中具有更优的电子/离子传输动力学特性,在尿素电合成过程中具有最高的电荷转移速率和最快的动力学反应。动力学研究表明,AlCuZn-0.5合金催化剂显著提升了尿素合成的活性。

图6     (a) AlCuZn,(b) AlCuZn-0.5和(c) AlCuZn-3.5的CV曲线;(d) ECSA曲线;(e) EIS图谱;(f)不同反应体系下的尿素法拉第效率和尿素产率图
Fig. 6     CV curves of (a) AlCuZn,(b) AlCuZn-0.5 and (c) AlCuZn-3.5 alloys;(d) ECSA curves;(e) EIS of AlCuZn,AlCuZn-0.5 and AlCuZn-3.5;(f) Faradaic efficiency for urea production and urea yield rate for different reaction systems

考虑到环境对实验结果的影响,进行了对照试验,以验证尿素生产的碳源和氮源。如图6(f)所示,在CO2饱和的KHCO3溶液与Ar饱和的KNO3溶液中,均未检测到尿素的生成。试验结果表明,只有在NO3和CO2共同存在的情况下,才能检测到尿素。这进一步证实了电催化产生的尿素是由CO2和NO3共还原生成的  Li K,Li Z B,Guo J,et al. Electrocatalytic synthesis of urea from carbon dioxide and nitrate over ZnO-based supported palladium-copper alloy catalysts [J]. Industrial & Engineering Chemistry Research,2025,64(30):14841-14849.
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3     结论

本文采用碱液刻蚀的方法,成功制备出多孔蜂窝状结构的AlCuZn合金,并将其应用于电催化CO2和NO3共还原合成尿素。在较低电压(–0.3 V vs. RHE)条件下,AlCuZn-0.5催化剂上尿素的法拉第效率高达65.7%,是原始AlCuZn的1.4倍;尿素产率为152.4 μg/(h·mgcat),是AlCuZn的1.8倍。循环稳定性测试表明,AlCuZn-0.5催化剂具有优异的循环稳定性和结构稳定性。电化学活性表面积以及电化学阻抗谱图分析表明,AlCuZn-0.5催化剂在电催化尿素合成中有更多的暴露活性位点、更高的传质效率和更小的电子传输阻力。可见,AlCuZn-0.5催化剂优异的电催化活性为CO2和NO3回收获得高附加值尿素产品提供了一种替代策略,具有良好的应用前景。

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