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南京工业大学 || 具有晶格畸变和表面重构特性的全非贵金属NiFeCuCo中熵合金气凝胶,实现高效稳定电催化分解水

  • 2026-04-21 08:19:22
南京工业大学 || 具有晶格畸变和表面重构特性的全非贵金属NiFeCuCo中熵合金气凝胶,实现高效稳定电催化分解水

气凝胶材料在线

随着传统化石燃料日益枯竭,利用地球上丰富的水资源,通过可再生能源驱动的水电解生产高纯度氢气,是未来可再生能源发展的关键途径之一。作为水分解过程的核心环节,阳极的氧析出反应(OER)涉及四电子-质子转移过程以及多种中间体的吸附/脱附反应动力学迟缓,是制约整体电解效率的瓶颈。目前,贵金属基氧化物(如RuO2IrO2仍是主流的商用催化剂,但其高昂成本与稀缺储量严重阻碍了大规模的商业应用。

近年来,研究人员通过合金化策略设计了一系列高性能的OER催化剂。这类材料兼具优异电导率、金属间协同效应以及耐腐蚀性,有望替代贵金属实现高效、稳定、低成本的电催化分解水。其中,NiFe基合金具有独特的价态转化特性,这使得在在阳极极化条件下,其表面重构为含可变价态的金属氧化物/羟基氧化物活性层,优化了催化活性位点,使其在碱性电解液中展现出高催化活性。

为了进一步提升OER活性,构筑三维多孔结构的合金基电催化剂成为重要研究方向。这种结构可有效提高质量传递效率、增加活性位点数量,进而提升催化性能。气凝胶作为由聚合物链或纳米颗粒组成的三维网络多孔材料,兼具高比表面积及自支撑特性。金属合金气凝胶融合了合金的本征高活性、气凝胶的结构稳定性,以及可调控的孔隙结构,被视为极具前景的OER催化材料。然而,中熵合金气凝胶(MEAA)在OER中的应用在当前的研究报道中仍较为有限,且制备过程的复杂性以及过渡金属的长期稳定性不足等问题亟待解决。

基于此,南京工业大学沈晓冬、崔升教授、吴晓栋副教授课题组采用金属粒子自组装结合冷冻干燥技术,制备了全非贵金属NiFeCuCo中熵合金气凝胶(NiFeCuCo MEAA)。它呈现出“珍珠链状”三维网络结构,并具有106.41 m2·g-1的高BET比表面积,这使活性位点得以充分暴露,并提供了丰富的扩散通道,促进了中间产物的有效扩散。此外,由于多金属诱导晶格畸变产生的协同效应,NiFeCuCo MEAA的内部应变场呈现出拉伸应力与压缩应力分布不规则的特征,可通过局域应变场调控活性位点的电子构型。此外,在1.0 M KOH电解液中表现出优异的OER电催化活性,在10mA·cm2电流密度下过电位仅为200 mV,且稳定性可达至少80小时。原位拉曼光谱测试表明,在OER过程中NiFeCuCo MEAA形成的NiOOH氧化层,在提升催化活性的同时,避免了内部结构受到进一步氧化和溶解,从而延长使用寿命。密度泛函理论(DFT)计算进一步表明,以Ni位点为主的多金属元素间的协同作用可调节电子结构和自旋态,显著降低中间体*O的结合强度,从而提升OER的催化性能。当NiFeCuCo MEAA用作阴离子交换膜水电解槽(AEMWE)装置时,在2.2 V电位下实现1.35A·cm2的高电流密度,电池效率可达79.8%。同时,利用NiFeCuCo MEAA组装的液态电解质锌空气电池(ZAB)具有200小时的充放电循环寿命。本研究提出一种通过调节电子结构来设计非贵金属气凝胶电催化剂的有效方法,为高效能源转换技术开辟了一条可行的途径。

相关研究成果以“Scalable Synthesis of a Cost-effective NiFeCuCo Medium-Entropy Alloy Aerogel with Lattice Distortion and Dynamic Surface Self-Reconstruction for Efficient Water Electrolysis”为题发表在Advanced Composites and Hybrid Materials期刊上。

原文链接

https://doi.org/10.1007/s42114-025-01599-1

研究内容

1.aNiFeCuCo MEAA制备示意图,(b)湿凝胶图像,(cXRD图谱,(d)氮脱附曲线和孔径分布曲线,(e)监测凝胶过程的紫外-可见吸收光谱,(f-h)通过MATLAB有限元分析模拟的金属颗粒生长与凝胶化过程,(i-jSEM图像,以及(kEDS能谱图。

2aTEM图像,(bHRTEM图像,(cSAED图,(dNiFeCuCo MEAA的晶格畸变分布,(e)基于GPA分析的内部应变图,所得样品的(fNi 2p、(gFe 2p、(hCu 2p,以及(iCo 2p的高分辨率XPS光谱。

3aLSV极化曲线,(b)塔菲尔曲线,(c)过电位直方图,(d)不同扫速下的电流密度,(eEIS Nyquist图,(f)质量活性和TOF的统计直方图,(gNiFeCuCo MEAA在恒定电流下的电位曲线,(h)经过OER后的SEM图像,以及(i)与文献报道的电催化剂的性能比较。

4. aNiFeCuCo MEAAOER中不同电压下的原位拉曼光谱,(bU=1.23 VOER四个基元步骤的吉布斯自由能曲线,(cNi、(dFe,(eCoPDOS,(f)电子变形密度等值面,(g)含有中间体*O的自旋电子密度切片(红色表示大值,蓝色表示小值),以及(hNi为活性位点时,NiFeNiFeCu AANiFeCuCo MEAAOER吉布斯自由能曲线。

5.aAEMWE装置示意图,(bLSV极化曲线,(c电池效率,dH2产率与法拉第效率的统计直方图,(eAEMWE的耐久性测试。(fZAB示意图,(g)功率密度,(h)放电电压,(i-kZAB为手机和灯泡供电照片,以及(j)恒电流充放电循环测试。

南京工业大学材料科学与工程学院沈晓冬教授、崔升教授与吴晓栋副教授为本工作的通讯作者,课题组博士生卢嘉欣为论文第一作者。

气凝胶材料在线

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  1. CONNECT:[ UseTime:0.000381s ] mysql:host=127.0.0.1;port=3306;dbname=b460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.000543s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.000240s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.000249s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.000475s ]
  6. SELECT * FROM `set` [ RunTime:0.000224s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.000499s ]
  8. SELECT * FROM `article` WHERE `id` = 520789 LIMIT 1 [ RunTime:0.002993s ]
  9. UPDATE `article` SET `lasttime` = 1776948428 WHERE `id` = 520789 [ RunTime:0.002641s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 65 LIMIT 1 [ RunTime:0.000237s ]
  11. SELECT * FROM `article` WHERE `id` < 520789 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.000427s ]
  12. SELECT * FROM `article` WHERE `id` > 520789 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.000370s ]
  13. SELECT * FROM `article` WHERE `id` < 520789 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.000655s ]
  14. SELECT * FROM `article` WHERE `id` < 520789 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.001236s ]
  15. SELECT * FROM `article` WHERE `id` < 520789 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.002462s ]
0.085910s