构建NiCu/Ni3N异质结构催化剂以实现碱性条件下高效氢氧化反应

doi:10.1016/S1872-2067(24)60142-7

催化学报 ›› 2024, Vol. 67: 186-193.DOI: 10.1016/S1872-2067(24)60142-7

构建NiCu/Ni₃N异质结构催化剂以实现碱性条件下高效氢氧化反应

李金池^a^,^d, 周万海^b, 于书棋^a^,^d, 卿晨^c, 何剑^a^,^d, 曾亮^c^,^d, 王尧^a^,^d(), 陈云贵^a^,^d

^a四川大学新能源与低碳技术研究院, 四川成都 610065
^b复旦大学化学与材料学院, 先进材料实验室, 上海 200433
^c四川大学材料科学与工程学院, 新能源材料系, 四川成都 610065
^d四川大学新能源材料与器件教育部工程研究中心, 四川成都 610065

收稿日期:2024-08-28 接受日期:2024-09-14 出版日期:2024-11-30 发布日期:2024-11-30
通讯作者: 王尧
基金资助:
国家自然科学基金(22279082)

Cu-induced interface engineering of NiCu/Ni₃N heterostructures for enhanced alkaline hydrogen oxidation reaction

Jinchi Li^a^,^d, Wanhai Zhou^b, Shuqi Yu^a^,^d, Chen Qing^c, Jian He^a^,^d, Liang Zeng^c^,^d, Yao Wang^a^,^d(), Yungui Chen^a^,^d

^aInstitute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610065, Sichuan, China
^bLaboratory of Advanced Materials, College of Chemistry and Materials, Fudan University, Shanghai 200433, China
^cDepartment of Advanced Energy Materials, College of Materials Science and Engineering, Sichuan University, Chengdu 610065, Sichuan, China
^dEngineering Research Center of Alternative Energy Materials & Devices, Ministry of Education, Chengdu 610065, Sichuan, China

Received:2024-08-28 Accepted:2024-09-14 Online:2024-11-30 Published:2024-11-30
Contact: Yao Wang
Supported by:
National Natural Science Foundation of China(22279082)

摘要/Abstract

摘要：

能源存储与转换装置在便携式电源、电动汽车和大规模能源存储等领域中扮演着至关重要的角色. 其中, 阴离子交换膜燃料电池(AEMFCs)因其高能量效率和可持续性, 逐渐成为可再生能源集成的理想选择. AEMFCs的优势在于可以在较低温度下操作, 同时具备较高的能量转化效率. 然而, 在实际应用中AEMFCs的性能仍主要依赖于贵金属催化剂, 如铂和铑. 这些贵金属催化剂虽然表现出优异的催化性能, 但其昂贵的成本限制了AEMFCs的大规模应用. 因此, 开发高效的非贵金属氢氧化反应(HOR)催化剂成为提高AEMFCs性能和降低成本的关键.

本文成功制备了NiCu/Ni₃N异质结构催化剂, 结合了NiCu合金和Ni₃N的协同优势, 显著优化了氢吸附能(HBE)和羟基吸附能(OHBE), 从而大幅度提高了HOR的催化活性. 不同于传统的通过调控焙烧条件来制备催化剂的方法, 本文采用调控Cu的掺杂含量实现异质结构的构建. 该方法不仅克服了传统方法的限制, 还为催化剂设计提供了新的思路. 研究发现, 当Cu掺杂量过多时, 会对Ni₃N的形成产生抑制作用, 导致Ni₃N仅在富Ni区域生成. 这种掺杂导致了在NiCu合金表面形成了平均粒径约为5 nm的小尺寸Ni₃N颗粒. X射线衍射、透射电子显微镜、X射线光电子能谱以及X射线吸收精细结构等表征结果证实了NiCu/Ni₃N异质结构成功合成. 电化学测试结果表明, NiCu/Ni₃N催化剂在0.1 mol L^‒1 KOH溶液中的氢氧化反应表现出较好的催化活性, 在50 mV的质量活性高达71.8 mA mg^‒1, 明显高于纯Ni和NiCu合金催化剂. 同时, 该催化剂的交换电流密度也显著提高, 表明其本征催化活性得到了显著增强. 稳定性测试结果显示, 该催化剂在经过1000次循环后, 其催化活性几乎没有衰减, 展现出较好的稳定性, 说明具有较强的实际应用性能. 为了深入理解催化性能的提升机制, 进行了密度泛函理论计算, 结果表明, NiCu/Ni₃N异质结构的独特界面可以降低氢氧化反应中关键步骤的能垒, 从而促进水的生成过程. 此外, 电子结构分析结果表明, 界面的形成有效地调节了Ni的d带中心, 优化了HBE和OHBE, 从而实现了对氢氧化反应活性的协同提升.

综上, 本文为构建具有优化界面结构的高性能非贵金属HOR催化剂提供了新的思路, 推进了AEMFCs在交通运输领域的应用. 未来, 进一步探索不同金属间的协同效应和界面工程, 将有助于开发更多高效、稳定的电催化材料.

关键词: 氢氧化反应, 异质结构电催化剂, 非贵金属催化剂, 氢吸附能, 羟基吸附能

Abstract:

Constructing well-defined interfaces in catalysts is a highly effective method to accelerate reactions with multiple intermediates. In this study, we developed a heterostructure catalyst combining fcc NiCu and hcp Ni₃N, aiming at achieving superior performance in alkaline hydrogen electrocatalysis. The NiCu/Ni₃N not only overcomes the inadequate hydroxyl binding energy performance of NiCu alloys but also solves the problems of insufficient active sites found in most Ni/Ni₃N. Experimental results and density functional theoretical calculations reveal that the formation of heterostructure significantly depends on the amount of Cu. This approach effectively prevents the side effects of increased catalyst particle size, typically resulting from the high temperatures and prolonged reaction times required for conventional synthesis of Ni/Ni₃N. The interface of this heterostructure induces a distinctive overlapping effect that enhances the adsorption of water and lowers the energy barrier for the rate-determining step. The NiCu/Ni₃N catalyst shows an impressive activity of 71.8 mA mg^-1 at an overpotential of 50 mV, a 14.7 times efficiency enhancement compared to pure Ni and comparable to that of low-loaded commercial Pt/C. This research highlights the potential of NiCu/Ni₃N in advancing catalyst development.

Key words: Hydrogen oxidation reaction, Heterostructured electrocatalyst, Non-precious metal catalyst, Hydrogen adsorption energy, Hydroxyl adsorption energy

李金池, 周万海, 于书棋, 卿晨, 何剑, 曾亮, 王尧, 陈云贵. 构建NiCu/Ni₃N异质结构催化剂以实现碱性条件下高效氢氧化反应[J]. 催化学报, 2024, 67: 186-193.

Jinchi Li, Wanhai Zhou, Shuqi Yu, Chen Qing, Jian He, Liang Zeng, Yao Wang, Yungui Chen. Cu-induced interface engineering of NiCu/Ni₃N heterostructures for enhanced alkaline hydrogen oxidation reaction[J]. Chinese Journal of Catalysis, 2024, 67: 186-193.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60142-7

https://www.cjcatal.com/CN/Y2024/V67/I12/186

图/表 4

Fig. 1. Morphological and Structural Characterization of NiCu/Ni3N Heterostructures and Pure Ni. (a) XRD patterns depicting the crystalline phases of the nanoparticles. (b) HRTEM images of NCu/Ni3N nanoparticles. (c) HRTEM images highlighting the heterojunctions within the NCu/Ni3N nanoparticles. (d) Projected density of states (pDOS) for surface Ni/Cu. (e) COHP analysis contrasting the bonding and antibonding interactions in Ni-N and Cu-N bonds. (f) The initial state, the transition state, the final state, and the corresponding energy differences for the formation process of Ni3N.

Fig. 2. Chemical state and atomic coordination environment of Ni, NiCu and NiCu/Ni3N. (a,b) Ni 2p XPS spectra and Cu 2p XPS spectra for pure Ni, NiCu, and NiCu/Ni3N. (c) N 1s XPS spectra for NiCu/Ni3N. (d) EXAFS at the Ni K-edge for Ni foil, NiO and the synthesized NiCu/Ni3N. (e) Fourier-transformed (FT) EXAFS for Ni foil, NiO and the synthesized NiCu/Ni3N. (f) The EXAFS fitting for NiCu/Ni3N. (g-i) Corresponding Wavelet transforms of the EXAFS spectra for NiCu/Ni3N, Ni foil and NiO.

Fig. 3. Electrochemical tests. (a) HOR polarization curves of NiCu/Ni3N, commercial Pt/C, Ni3N, NiCu and pure Ni in H2-saturated 0.1 mol L−1 KOH. (b) Linear fitting curves in the micro-polarization region (−5 to 5 mV) demonstrating the exchange current densities. (c) Tafel plots of NiCu/Ni3N, commercial Pt/C, Ni3N, NiCu and pure Ni corresponding to the Butler-Volmer fitting. (d) HOR polarization curves of NiCu/Ni3Ncatalyst at varied rotational speeds. The inset curve is the Koutecky-Levich (K-L) plot. (e) HOR polarization curves for NiCu/Ni3N, NiCu, and Pure Ni in H2-saturated 0.1 mol L−1 KOH were measured over a potential range of 0-0.5 V to test the potential for failure. (f) HOR polarization curves of NiCu/Ni3N before and after 1000 cycles, underlining the remarkable stability of the catalyst.

Fig. 4. DFT calculation. (a) Schematic representations of different adsorption sites for hydrogen atoms on the NiCu(111)Ni3N(002) model. (b) pDOS detailing the d-band centers of Ni at varying active sites. (c) The calculated free energy of hydrogen adsorption (ΔGM*H) on two distinct facets of NiCu(111)/Ni3N(002). (d) Differential charge density at the interface of NiCu(111)/Ni3N(002), highlighting electron donation and withdrawal zones. (e) COHP analyses of the Ni−O(OH) bonds. (f) Energy profile delineating the initial, transition, and final states in the water formation process, with associated energy differences. Gray balls, Ni atoms; Blue balls, Cu atoms; Light blue balls, N atoms; Pink, H atoms.

参考文献

[1]	X. Bai, J. Han, S. Chen, X. Niu, J. Guan, Chin. J. Catal., 2023, 54, 212-219.
[2]	X. Bai, J. Guan, Chin. J. Catal., 2022, 43, 2057-2090.
[3]	L. Xiao, Z. Wang, J. Guan, Adv. Funct. Mater., 2024, 34, 2310195.
[4]	L. Huang, H. Niu, C. Xia, F. M. Li, Z. Shahid, B. Y. Xia, Adv. Mater., 2024, 36, 2404773.
[5]	L. Xiao, L. Qi, J. Sun, A. Husile, S. Zhang, Z. Wang, J. Guan, Nano Energy, 2023, 120, 109155.
[6]	X. Bai, Y. Wang, J. Han, X. Niu, J. Guan, Appl. Catal. B, 2023, 337, 122966.
[7]	T. Yang, Z. Chen, Y. Yang, S. Zhao, Joule, 2024, 8, 287-290.
[8]	M. Wang, H. Yang, J. Shi, Y. Chen, Y. Zhou, L. Wang, S. Di, X. Zhao, J. Zhong, T. Cheng, W. Zhou, Y. Li, Angew. Chem. Int. Ed., 2021, 60, 5771-5777.
[9]	J. K. Nørskov, T. Bligaard, A. Logadottir, J. Kitchin, J. G. Chen, S. Pandelov, U. Stimming, J. Electrochem. Soc., 2005, 152, J23-J26.
[10]	W. Sheng, A. P. Bivens, M. Myint, Z. Zhuang, R. V. Forest, Q. Fang, J. G. Chen, Y. Yan, Energy Environ. Sci., 2014, 7, 1719-1724.
[11]	P.-P. Yang, X.-L. Zhang, P. Liu, D. J. Kelly, Z.-Z. Niu, Y. Kong, L. Shi, Y.-R. Zheng, M.-H. Fan, H.-J. Wang, M.-R. Gao, J. Am. Chem. Soc., 2023, 145, 8714-8725.
[12]	Y. Jia, H.-S. Hsu, W.-C. Huang, D.-W. Lee, S.-W. Lee, T.-Y. Chen, L. Zhou, J.-H. Wang, K.-W. Wang, S. Dai, Nano Lett., 2023, 23, 2262-2268.
[13]	O. V. Cherstiouk, P. A. Simonov, A. G. Oshchepkov, V. I. Zaikovskii, T. Y. Kardash, A. Bonnefont, V. N. Parmon, E. R. Savinova, J. Electroanal. Chem., 2016, 783, 146-151.
[14]	J. Durst, C. Simon, F. Hasché, H. A. Gasteiger, J. Electrochem. Soc., 2014, 162, F190-F203.
[15]	J. K. Nørskov, T. Bligaard, B,. Hvolbæk, F. Abild-Pedersen, I. Chorkendorff, C. H. Christensen, Chem. Soc. Rev., 2008, 37, 2163-2171.
[16]	F. Yang, X. Bao, P. Li, X. Wang, G. Cheng, S. Chen, W. Luo, Angew. Chem. Int. Ed., 2019, 58, 14179-14183.
[17]	S. Qin, Y. Duan, X.-L. Zhang, L.-R. Zheng, F.-Y. Gao, P.-P. Yang, Z.-Z. Niu, R. Liu, Y. Yang, X.-S. Zheng, J.-F. Zhu, M.-R. Gao, Nat. Commun., 2021, 12, 2686.
[18]	W. Ni, T. Wang, F. Héroguel, A. Krammer, S. Lee, L. Yao, A. Schüler, J. S. Luterbacher, Y. Yan, X. Hu, Nat. Mater., 2022, 21, 804-810.
[19]	X. Zhao, X. Li, L. An, L. Zheng, J. Yang, D. Wang, Angew. Chem. Int. Ed., 2022, 61, e202206588.
[20]	I. C. Gerber, P. Serp, Chem. Rev., 2019, 120, 1250-1349.
[21]	Y. Yang, X. Sun, G. Han, X. Liu, X. Zhang, Y. Sun, M. Zhang, Z. Cao, Y. Sun, Angew. Chem. Int. Ed., 2019, 58, 10644-10649.
[22]	F. Song, W. Li, J. Yang, G. Han, P. Liao, Y. Sun, Nat. Commun., 2018, 9, 4531.
[23]	X. Gao, X. Liu, W. Zang, H. Dong, Y. Pang, Z. Kou, P. Wang, Z. Pan, S. Wei, S. Mu, J. Wang, Nano Energy, 2020, 78, 105355.
[24]	L. Xiong, Y. Qiu, H. Dong, B. Gao, X. Zhang, P. K. Chu, X. Peng, Int. J. Hydrogen Energy, 2024, 59, 400-407.
[25]	M. Yan, K. Mao, P. Cui, C. Chen, J. Zhao, X. Wang, L. Yang, H. Yang, Q. Wu, Z. Hu, Nano Res., 2020, 13, 28-334.
[26]	G. Jiang, X. Shi, M. Cui, W. Wang, P. Wang, G. Johnson, Y. Nie, X. Lv, X. Zhang, F. Dong, S. Zhang, ACS Appl. Mater. Interfaces, 2021, 13, 4072-4083.
[27]	X. Xu, X. Hou, P. Du, C. Zhang, S. Zhang, H. Wang, A. Toghan, M. Huang, Nano Res., 2022, 15, 7124-7133.
[28]	W. H. Li, J. Yang, D. Wang, Angew. Chem., 2022, 134, e202213318.
[29]	T. Tang, X. Bai, Z. Wang, J. Guan, Chem. Sci., 2024, 15, 5082-5112.
[30]	L.-Y. Xiao, Z. Wang, J. Guan, Chem. Sci., 2023, 14, 12850-12868.
[31]	B. Zhang, J. Wang, G. Liu, C. M. Weiss, D. Liu, Y. Chen, L. Xia, P. Zhou, M. Gao, Y. Liu, J. Chen, Y. Yan, M. Shao, H. Pan, W. Sun, Nat. Catal., 2024, 7, 441-451.
[32]	Z. Qi, Y. Zeng, Z. Hou, W. Zhu, B. Wei, Y. Yang, B. Lin, H. Liang, Nano Res., 2023, 16, 4803-4811.
[33]	D. Zhang, H. Li, A. Riaz, A. Sharma, W. Liang, Y. Wang, H. Chen, K. Vora, D. Yan, Z. Su, A. Tricoli, C. Zhao, F. J. Beck, K. Reuter, K. Catchpole, S. Karuturi, Energy Environ. Sci., 2022, 15, 185-195.
[34]	Y. Men, X. Su, P. Li, Y. Tan, C. Ge, S. Jia, L. Li, J. Wang, G. Cheng, L. Zhuang, S. Chen, W. Luo, J. Am. Chem. Soc., 2022, 144, 12661-12672.
[35]	Y. Wu, Y. Xie, S. Niu, Y. Zang, J. Cai, Z. Bian, X. Yin, Y. Fang, D. Sun, D. Niu, Z. Lu, A. Mosallanezhad, H. Wang, D. Rao, H. Pan, G. Wang, Nano Res., 2021, 14, 3458-3465.
[36]	A. G. Oshchepkov, A. Bonnefont, S. N. Pronkin, O. V. Cherstiouk, C. Ulhaq-Bouillet, V. Papaefthimiou, V. N. Parmon, E. R. Savinova, J. Power Sources, 2018, 402, 447-452.
[37]	X. Tian, R. Ren, F. Wei, J. Pei, Z. Zhuang, L. Zhuang, W. Sheng, Nat. Commun., 2024, 15, 76.
[38]	W. Wang, Y. Zhuang, Z. Wang, Y. Zhang, X. Zhong, N. An, G. Zhang, Mater. Lett., 2009, 63, 2432-2434.

构建NiCu/Ni₃N异质结构催化剂以实现碱性条件下高效氢氧化反应

Cu-induced interface engineering of NiCu/Ni₃N heterostructures for enhanced alkaline hydrogen oxidation reaction

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 4

参考文献

相关文章 11

编辑推荐

Metrics

[1]	陈瑞, 方翔, 张东方, 赫兰齐, 吴胤龙, 孙成华, 王昆, 宋树芹. 原位构筑三维有序自支撑Co-N-C一体化电极并用于高效电催化氧还原反应[J]. 催化学报, 2024, 61(6): 237-246.
[2]	杨玉婷, 石路岩, 梁沁睿, 刘奕, 董家新, 王宝, 杨秀林. 构筑富含磷空位缺陷的磷化钯催化剂实现高效和抗CO毒化的碱性氢氧化反应[J]. 催化学报, 2024, 56(1): 176-187.
[3]	田芸睿, 谭皓天, 李霞, 贾晶晶, 毛子贤, 刘健, 梁骥. 用于氨电氧化反应生成硝酸盐/亚硝酸盐的金属基电催化剂：过去、现在和未来[J]. 催化学报, 2024, 56(1): 25-50.
[4]	李鹏, 赵国强, 程宁燕, 夏力学, 李晓宁, 陈亚平, 劳梦梦, 程振祥, 赵焱, 徐迅, 姜银珠, 潘洪革, 窦士学, 孙文平. 过渡金属单原子功能化碳载体促进碱性氢电催化反应动力学[J]. 催化学报, 2022, 43(5): 1351-1359.
[5]	安露露, 邓邵峰, 郭煦昀, 刘旭坡, 赵桐辉, 陈科, 朱叶, 付玉喜, 赵旭, 王得丽. Ni₃N/MoO₂平面异质结构实现增强的碱性氢氧化[J]. 催化学报, 2022, 43(12): 3154-3160.
[6]	徐才丽, 陈倩, 丁蓉, 黄生田, 张云, 樊光银. 可持续固相合成高分散PdAg合金纳米颗粒用于电催化氢氧化和氢析出反应[J]. 催化学报, 2021, 42(2): 251-258.
[7]	仇暘, 谢小红, 李文震, 邵玉艳. 碱性介质中氢氧化反应电催化剂的开发: 从机理认识到材料设计[J]. 催化学报, 2021, 42(12): 2094-2104.
[8]	周君慧, 刘冠兰, 姜全国, 赵伟娜, 敖志敏, 安太成. 单原子催化剂Ti/Ti₃C₂O₂催化氧化甲醛的密度泛函理论研究[J]. 催化学报, 2020, 41(10): 1633-1644.
[9]	陈驰, 周志有, 王宇成, 张雪, 杨晓冬, 张新胜, 孙世刚. 以CaCl₂为模板合成的高活性和高稳定性铁、氮、硫共掺杂多孔碳氧还原电催化剂[J]. 催化学报, 2017, 38(4): 673-682.
[10]	廖建华, 丁炜, 陶思成, 聂瑶, 李巍, 吴光平, 陈四国, 李莉, 魏子栋. 碳载合金IrM(M=Fe,Ni,Co)纳米颗粒催化酸性与碱性介质中氢氧化反应[J]. 催化学报, 2016, 37(7): 1142-1148.
[11]	白杨芝, 衣宝廉, 李佳, 蒋尚峰, 张洪杰, 邵志刚, 宋玉江. 以金属有机骨架为前驱体的高活性氧还原非贵金属催化剂制备[J]. 催化学报, 2016, 37(7): 1127-1133.