构建用于工业电流密度下高效电解尿素辅助制氢的Ni2P/CoP界面催化剂

doi:10.1016/S1872-2067(24)60198-1

催化学报 ›› 2025, Vol. 69: 163-175.DOI: 10.1016/S1872-2067(24)60198-1

构建用于工业电流密度下高效电解尿素辅助制氢的Ni₂P/CoP界面催化剂

陆博荣^a^,¹, 吕春梅^a^,¹, 谢颖^d, 朱凯^a, 叶克^a^,^b^,^*(), 李晓锦^b^,^c^,^*()

^a哈尔滨工程大学材料科学与化学工程学院, 超轻材料与表面技术教育部重点实验室, 黑龙江哈尔滨 150001
^b中国科学院青岛生物能源与过程研究所, 山东青岛 266101
^c山东能源研究院, 山东青岛 266101
^d黑龙江大学化学与材料科学学院, 黑龙江哈尔滨 150080

收稿日期:2024-09-07 接受日期:2024-11-12 出版日期:2025-02-18 发布日期:2025-02-10
通讯作者: *电子信箱: yeke@hrbeu.edu.cn (叶克), lixj@qibebt.ac.cn (李晓锦)
作者简介:第一联系人：
¹共同第一作者.
基金资助:
国家重点研发计划(2021YFB4001700);山东省自然科学基金-重大基础研究项目(ZR2022ZD10);青岛市自然科学基金(23-2-1-221-zyyd-jch);QIBEBT国际合作项目(QIBEBT ICP202303);青岛新能源山东省实验室开放课题(QNESL OP 202303)

Construction of Ni₂P/CoP interface for highly efficient electrolysis of urea-assisted hydrogen production at industrial current densities

Borong Lu^a^,¹, Chunmei Lv^a^,¹, Ying Xie^d, Kai Zhu^a, Ke Ye^a^,^b^,^*(), Xiaojin Li^b^,^c^,^*()

^aKey Laboratory of Superlight Materials and Surface Technology of Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, Heilongjiang, China
^bQingdao New Energy Shandong Laboratory, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, Shandong, China
^cShandong Energy Institute, Qingdao 266101, Shandong, China
^dKey Laboratory of Functional Inorganic Material Chemistry of Ministry of Education, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, Heilongjiang, China

Received:2024-09-07 Accepted:2024-11-12 Online:2025-02-18 Published:2025-02-10
Contact: *E-mail: yeke@hrbeu.edu.cn (K. Ye), lixj@qibebt.ac.cn (X. Li).
About author:First author contact:
¹ Contributed equally to this work.
Supported by:
National High Technology Research and Development Program of China(2021YFB4001700);Major Fundamental Research Program of Natural Science Foundation of Shandong Province(ZR2022ZD10);Qingdao Natural Science Foundation(23-2-1-221-zyyd-jch);QIBEBT INTERNATIONAL COOPERATION Project(QIBEBT ICP202303);Qingdao New Energy Shandong Laboratory Open Project(QNESL OP 202303)

摘要/Abstract

摘要：

尿素氧化反应(UOR)是尿素辅助电解水制氢的阳极反应, 可以替代水电解中的阳极析氧反应, 在低能耗制氢的同时对尿素废水进行降解. 因此, 近年来UOR作为一种具有前景的可持续清洁能源技术, 受到了广泛关注. 然而由于UOR存在复杂的反应过程, 动力学缓慢以及催化剂稳定性较差等问题, 需要开发具有高活性和高稳定性的催化剂. 界面化学调控策略被认为是制备UOR催化剂的有效方法.然而, 传统的界面催化剂通常受限于各组分本身的固有活性和不兼容性, 而且界面间不规则的电荷分布和缓慢的电荷转移速率严重限制了UOR的活性.

本文报道了一种Ni₂P/CoP界面催化剂, 首先通过密度泛函理论(DFT)计算预测Ni₂P/CoP界面间电荷自发地从CoP转移到Ni₂P, 并且具有电荷调节能力, 低Gibbs自由能的潜在反应决定步骤则证明了界面的构建可能提高其催化活性. 随后通过水热、溶剂热和磷化法合成了Ni₂P/CoP催化剂. X射线衍射、扫描电镜和透射电镜等结果表明Ni₂P/CoP被成功合成, 并且在高分辨透射电镜图中存在明显的晶界特征, 结合DFT预测的功函数(Ф)和X射线吸收精细结构谱的分析结果, 表明Ni₂P/CoP界面的成功构建. 原位电化学阻抗谱、准原位X射线光电子能谱和准原位拉曼光谱结果表明, Ni₂P/CoP通过界面间形成的内置电场, 加速电荷定向转移, 促进UOR过程. 采用原位电化学光学显微镜评估了Ni₂P/CoP在析氢反应过程中的气体释放程度, 结果表明, Ni₂P/CoP具有快速的气体逸出速率. 分别在6 mol L^‒1 KOH + 0.5 mol L^‒1尿素和尿液(6 mol L^‒1 KOH)的电解液中, 使用Ni₂P/CoP同时作为阴极和阳极分别在尿素电解(UOR||HER)和人体尿液电解(HUOR||HER)体系中进行计时电位测试, 在Ni₂P/CoP在500 mA cm⁻²电流密度下, 分别以1.70和1.90 V的较小恒定电池电压下持续工作120和50 h, 表现出高活性和稳定性. 通过紫外-可见吸收光谱和二乙酰一肟-安替比林法(国家标准方法)评估了Ni₂P/CoP对尿素降解的效果, 结果表明, Ni₂P/CoP的尿素降解率为73.1%, 表明Ni₂P/CoP具有电化学降解富含尿素废水的潜力.

综上所述, 本文通过DFT预测, 合理的使用界面化学调制策略, 优化了Ni₂P/CoP催化剂界面间电荷分布, 为工业级大规模尿素废水电解辅助制氢和用于绿色能源转化催化剂的开发提供新思路.

关键词: 界面化学策略, 理论预测, 先进界面构造, 定向电荷转移, 尿素氧化反应

Abstract:

Interface chemical modulation strategies are considered as promising method to prepare electrocatalysts for the urea oxidation reaction (UOR). However, conventional interface catalysts are generally limited by the inherent activity and incompatibility of the individual components themselves, and the irregular charge distribution and slow charge transfer ability between interfaces severely limit the activity of UOR. Therefore, we optimized and designed a Ni₂P/CoP interface with modulated surface charge distribution and directed charge transfer to promote UOR activity. Density functional theorycalculations first predict a regular charge transfer from CoP to Ni₂P, which creates a built-in electric field between Ni₂P and CoP interface. Optimization of the adsorption/desorption process of UOR/HER reaction intermediates leads to the improvement of catalytic activity. Electrochemical impedance spectroscopy and ex situ X-ray photoelectron spectroscopy characterization confirm the unique mechanism of facilitated reaction at the Ni₂P/CoP interface. Electrochemical tests further validated the prediction with excellent UOR/HER activities of 1.28 V and 19.7 mV vs. RHE, at 10 mA cm^-2, respectively. Furthermore, Ni₂P/CoP achieves industrial-grade current densities (500 mA cm^-2) at 1.75 V and 1.87 V in the overall urea electrolyzer (UOR||HER) and overall human urine electrolyzer (HUOR||HER), respectively, and demonstrates considerable durability.

Key words: Interface chemical strategy, Theoretical predictions, Advanced interface construction, Directed charge transfer, Urea oxidation reaction

陆博荣, 吕春梅, 谢颖, 朱凯, 叶克, 李晓锦. 构建用于工业电流密度下高效电解尿素辅助制氢的Ni₂P/CoP界面催化剂[J]. 催化学报, 2025, 69: 163-175.

Borong Lu, Chunmei Lv, Ying Xie, Kai Zhu, Ke Ye, Xiaojin Li. Construction of Ni₂P/CoP interface for highly efficient electrolysis of urea-assisted hydrogen production at industrial current densities[J]. Chinese Journal of Catalysis, 2025, 69: 163-175.

×
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)60198-1

https://www.cjcatal.com/CN/Y2025/V69/I2/163

图/表 6

Fig. 1. (a) Schematic representation of directional charge transfer at the Ni2P/CoP interface. (b) TDOS of CoP, Ni2P, and Ni2P/CoP. (c) The work function of CoP, Ni2P, and Ni2P/CoP. (d) Schematic diagram of Ф for CoP and Ni2P. (e) Schematic of electron transfer from CoP to Ni2P. (f) Gibbes free energy diagrams of various catalysts for the adsorption of H*. (g) Gibbes free energy diagrams of various catalysts during UOR processes.

Fig. 2. (a) Schematic diagram of preparation process of Ni2P/CoP. The SEM images of Ni2P (b,c) and Ni2P/CoP (d,e). TEM (f,g) and the HRTEM (h) images of Ni2P/CoP. HAADF (i) and the EDS mapping (j-l) images of Ni2P/CoP (Ni, Co, P elements).

Fig. 3. Characterization of the electronic structure of Ni2P/CoP. XPS spectra: Co 2p (a), Ni 2p (b), and Co 2p (c) of CoP and Ni2P/CoP. XAFS characterizations: (d) normalized XANES spectra of Co K-edge. (e) FT-EXAFS spectra at the Co K-edge. (f) WT plots for the k3-weighted EXAFS signals of Co K-edge for Ni2P/CoP. (g) Normalized XANES spectra of Ni K-edge. (h) Corresponding FT-EXAFS spectra. (i) WT plots for the k3-weighted EXAFS signals of Co K-edge for CoP.

Fig. 4. (a) The LSV plots (with iR compensation) for the OER and UOR of Ni2P/CoP with a scan rate of 5 mV s-1. (b) UOR LSV plots of related catalysts in 1 mol L?1 KOH with 0.5 mol L?1 urea. (c) Tafel slopes. (d) The measurements of Cdl. (e) Corresponding ECSA. (f) The LSV plots for HER of Ni2P/CoP and other electrocatalysts with a scan rate of 5 mV s-1 in 1 mol L?1 KOH. (g) Corresponding Tafel Slope. (h) Exchange current density (j0) of electrocatalysts. (i) The measurements of Cdl.

Fig. 5. (a) LSV plots of Ni2P/CoP in HER||UOR and HER||OER. (b) LSV plots of Ni2P/CoP and catalysts in HER||UOR. (c) Comparison of HER||UOR performance with previously reported catalysts. (d) LSV plots in HER||HUOR. (e) UV spectrum of Ni2P/CoP. (f) Corresponding urea degradation rate. (g) Faradaic efficiency in systems HER||UOR and HER||HUOR. (h) Chronopotentiometry tests of Ni2P/CoP in HER||UOR and HER||HUOR under 500 mA c?2.

Fig. 6. (a,b) Dynamic evaluation of the UOR reaction mechanism of catalysts: advanced UOR reaction mechanism diagram for Ni2P/CoP interface. Bode plots of Ni2P (c), CoP (d), and Ni2P/CoP (e). Ex situ XPS analysis for Ni 2p of Ni2P/CoP (f) and (g). (h?j) In situ optical microscopy of Ni2P/CoP during the dynamics of the HER reaction.

参考文献

[1]	A. L. Li, S. Kong, K. Adachi, H. Ooka, K. Fushimi, Q. Jiang, H. Ofuchi, S. Hamamoto, M. Oura, K. Higashi, T. Kaneko, T. Uruga, N. Kawamura, D. Hashizume, R. Nakamura, Science, 2024, 384, 666-670.
[2]	T. Wang, L. Tao, X. Zhu, C. Chen, W. Chen, S. Du, Y. Zhou, B. Zhou, D. Wang, C. Xie, P. Long, W. Li, Y. Wang, R. Chen, Y. Zou, X. Z. Fu, Y. Li, X. Duan, S. Wang, Nat. Catal., 2021, 5, 66-73.
[3]	C. J. Deng, C. F. Qi, X. M. Wu, G. H. Jing, H. W. Zhao, Green Carbon, 2024, 2, 124-130.
[4]	T. Zhao, B. Gong, G. Xu, J. Jiang, L. Zhang, Chin. J. Catal., 2024, 61, 269-280.
[5]	B. R. Lu, C. M. Lv, Y. Xie, L. X. Gao, J. Yan, K. Zhu, G. L. Wang, D. X. Cao, K. Ye, Small, 2023, 19, 2302923.
[6]	Q. Lv, W. Zhang, Z. Long, J. Wang, X. Zou, W. Ren, L. Hou, X. Lu, Y. Zhao, X. Yu, X. Li, Chin. J. Catal., 2024, 62, 254-264.
[7]	X. Q. Gao, Y. D. Chen, T. S. J. M. Huang, W. Zhang, Q. Wang, R. Cao, Energy Environ. Sci., 2020, 13, 174-182.
[8]	X. Y. Peng, M. C. Zhang, H. N. Qin, J. X. Han, Y. H. Xu, W. Z. Li, X. P. Zhang, W. Zhang, U. Apfel, R. Cao, Angew. Chem. Int. Ed., 2024, 63, e202401074.
[9]	B. R. Lu, Z. Li, J. L. Yin, K. Zhu, K. Ye, Appl. Catal. B, 2024, 350, 123940.
[10]	J. Y. Chen, Y. K. Kang, W. Zhang, Z. H. Zhang, Y. Chen, Y. Yang, L. L. Duan, Y. F. Li, W. Li, Angew. Chem. Int. Ed., 2022, 61, e202203022.
[11]	Y. Tong, P. Z. Chen, M. X. Zhang, T. P. Zhou, L. D. Zhang, W. S. Chu, C. Z. Wu, Y. Xie, ACS Catal., 2018, 8, 1-7.
[12]	N. Wang, X. P. Zhang, J. Han, H. Lei, Q. Zhang, H. Zhang, W. Zhang, U. Apfel, R. Cao, Chin. J. Catal., 2023, 45, 88-94.
[13]	G. Li, G. Han, L. Wang, X. Cui, N. K. Moehring, P. R. Kidambi, D. E. Jiang, Y. Sun, Nat. Commun., 2023, 14, 525.
[14]	B. Huang, J. N. Wang, D. L. Xie, Q. P. Huang, D. Wen, X. Q. Zeng, D. M. Lin, W. H. Guo, H. C. Sun, F. Y. Xie, Chem. Eng. J., 2024, 498, 155006.
[15]	Y. M. Zhou, B. X. Chu, Z. J. Sun, L. H. Dong, F. Wang, B. Li, M. G. Fan, Z. J. Chen, Appl. Catal. B, 2023, 323, 122168.
[16]	R. J. Luo, Q. F. Guo, Z. H. Tang, M. M. Zhang, X. X. Li, B. Gao, X. M. Zhang, K. F. Huo, Y. Zheng, Adv. Funct. Mater., 2023, 33, 2306115.
[17]	B. R. Lu, Y. L. Jing, J. L. Yin, K. Zhu, K. Ye, X. J. Li, J. Power Sources, 2024, 615, 235065.
[18]	H. Y. Yang, P. V. Menezes, G. L. Dai, G. Vijaykumar, Z. L. Chen, M. Al-Shakran, T. Jacob, M. Driess, P. W. Menezes, Appl. Catal. B, 2023, 324, 122249.
[19]	Y. J. Pan, Z. C. Wang, K. X. Wang, Q. Ye, B. S. Shen, F. S. Yang, Y. L. Cheng, Adv. Funct. Mater., 2024, 34, 2402264.
[20]	T. T. Liu, Y. C. Wang, Y. Z. Wang, M. S. Cao, Adv. Funct. Mater., 2024, 10.1002/adfm.202404280.
[21]	X. C. Xu, H. J. Liao, L. Huang, S. J. Chen, R. Wang, S. Wu, Y. X. Wu, Z. P. Sun, H. T. Huang, Appl. Catal. B, 2024, 341, 123312.
[22]	X. B. Zheng, J. R. Yang, P. Li, Z. L. Jiang, P. Zhu, Q. S. Wang, J. B. Wu, E. Zhang, W. P. Sun, S. X. Dou, D. S. Wang, Y. D. Li, Angew. Chem. Int. Ed., 2023, 62, e202217449.
[23]	L. Reith, C. A. Triana, F. Pazoki, M. Amiri, M. Nyman, G. R. Patzke, J. Am. Chem. Soc., 2021, 143, 15022-15038.
[24]	R. Boppella, J. W. Tan, W. Yang, J. Moon, Adv. Funct. Mater., 2019, 29, 1807976.
[25]	J. F. Xie, L. Gao, S. S. Cao, W. W. Liu, F. C. Lei, P. Hao, X. Y. Xia, B. Tang, J. Mater. Chem. A, 2019, 7, 13577-13584.
[26]	W. Kang, R. Wei, H. Yin, D. Li, Z. Chen, Q. Huang, P. Zhang, H. Jing, X. Wang, C. Li, J. Am. Chem. Soc., 2023, 145, 3470-3477.
[27]	L. N. Sha, K. Ye, J. L. Yin, K. Zhu, K. Cheng, J. Yan, G. L. Wang, D. X. Cao, Chem. Eng. J., 2020, 381, 122603.
[28]	Y. L. Dang, J. K. He, T. L. Wu, L. P. Yu, P. Kerns, L. Y. Wen, J. Ouyang, S. L. Suib, ACS Appl. Mater. Interfaces, 2019, 11, 29879-29887.
[29]	H. Liu, X. Ma, H. Hu, Y. Y. Pan, W. N. Zhao, J. L. Liu, X. Y. Zhao, J. L. Wang, Z. X. Yang, Q. S. Zhao, H. Ning, M. B. Wu, ACS Appl. Mater. Interfaces, 2019, 11, 15528-15536.
[30]	L. Fu, J. Zhou, Z. L. Zhou, B. Xiao, N. Khaorapapong, Y. Q. Kang, K. Wu, Y. Yamauchi, ACS Nano, 2023, 17, 22744-22754.
[31]	J. Y. Wang, Y. Fu, W. B. Kong, S. Q. Li, C. K. Yuan, J. R. Bai, X. Chen, J. Zhang, Y. H. Sun, ACS Catal., 2022, 12, 4382-4393.
[32]	F. Zhang, J. Ma, Y. Tan, G. Yu, H. X. Qin, L. R. Zheng, H. B. Liu, R. Li, ACS Catal., 2022, 12, 5827-5833.
[33]	Y. Lin, K. Sun, S. J. Liu, X. M. Chen, Y. S. Cheng, W. C. Cheong, Z. Chen, L. R. Zheng, J. Zhang, X. Y. Li, Y. Pan, C. Chen, Adv. Energy Mater., 2019, 9, 1901213.
[34]	S. J. Shen, Z. P. Wang, Z. P. Lin, K. Song, Q. H. Zhang, F. Q. Meng, L. Gu, W. W. Zhong, Adv. Mater., 2022, 34, 2110631.
[35]	H. N Jia, N. Yao, C. Yu, H. J. Cong, W. Luo, Angew. Chem. Int. Ed., 2023, 62, e202313886.
[36]	T. Wang, H. M. Wu, C. Q. Feng, L. Zhang, J. J. Zhang, J. Mater. Chem. A, 2020, 8, 18106-18116.
[37]	A. Kumar, X. H. Liu, J. S. Lee, B. Debnath, A. R. Jadhav, X. D. Shao, V. Q. Bui, Y. Hwang, Y. Liu, M. G. Kim, H. Y. Lee, Energy Environ. Sci., 2021, 14, 6494-6505.
[38]	P. Li, M. Wang, X. Duan, L. Zheng, X. Cheng, Y. Zhang, Y. Kuang, Y. Li, Q. Ma, Z. Feng, W. Liu, X. Sun, Nat. Commun., 2019, 10, 1711.
[39]	G. F. Qian, J. L. Chen, W. J. Jiang, T. Q. Yu, K. X. Tan, S. B. Yin, Carbon Energy, 2023, 5, e368.
[40]	H. C. Sun, W. Zhang, J. G. Li, Z. S. Li, X. Ao, K. H. Xue, K. Ostrikov, J. Tang, C. D. Wang, Appl. Catal. B, 2021, 284, 119740.
[41]	Z. L. Wang, W. J. Liu, Y. M. Hu, M. L. Guan, L. Xu, H. P. Li, J. Bao, H. M. Li, Appl. Catal. B, 2020, 272, 118959.
[42]	X. D. Ding, L. S. Pei, Y. X. Huang, D. Y. Chen, Z. L. Xie, Small, 2022, 18, 2205547.
[43]	X. F. Xu, H. Ullah, M. Humayun, L. F. Li, X. Zhang, M. Bououdina, D. P. Debecker, K. F. Huo, D. Wang, C. C. Wang, Adv. Funct. Mater., 2023, 33, 2303986.
[44]	Z. Y. Yu, C. C. Lang, M. R. Gao, Y. Chen, Q. Q. Fu, Y. Duan, S. H. Yu, Energy Environ. Sci., 2018, 11, 1890-1897.
[45]	T. T. Liu, D. N. Liu, F. L. Qu, D. X. Wang, L. Zhang, R. X. Ge, S. Hao, Y. J. Ma, G. Du, A. Asiri, L. Chen, X. P. Sun, Adv. Energy Mater., 2017, 7, 1700020.
[46]	M. Y. Liu, W. H. Zou, J. Cong, N. Su, S. L. Qiu, L. X. Hou, Small, 2023, 19, 2302698.
[47]	C. Wang, H. L. Lu, Z. Y. Mao, C. L. Yan, G. Z. Shen, X. F. Wang, Adv. Funct. Mater., 2020, 30, 2000556.
[48]	S. J. Patil, N. R. Chodankar, S. Hwang, G. Rama Raju, Y. Huh, Y. K. Han, Small, 2021, 18, 2103326.
[49]	K. X. Li, B. B. Xie, D. M. Feng, Y. Tong, ChemSusChem, 2022, 15, e202201656.
[50]	Y. Qi, Y. Zhang, L. Yang, Y. Zhao, Y. Zhu, H. Jiang, C. Li, Nat. Commun., 2022, 13, 4602.
[51]	H. Y. Wang, S. F. Hung, H. Y. Chen, T. S. Chan, H. M. Chen, B. Liu, J. Am. Chem. Soc., 2016, 138, 36-39.
[52]	Y. Lu, T. Liu, C. L. Dong, C. Yang, L. Zhou, Y. C. Huang, Y. Li, B. Zhou, Y. Zou, S. Wang, Adv. Mater., 2022, 34, 2107185.
[53]	X. Jia, H. Kang, X. Yang, Y. Li, K. Cui, X. Wu, W. Qin, G. Wu, Appl. Catal. B, 2022, 312, 121389.
[54]	H. Qin, Y. Ye, J. Li, W. Jia, S. Zheng, X. Cao, G. Lin, L. Jiao, Adv. Funct. Mater., 2023, 33, 2209698.
[55]	M. Y. Liu, W. H. Zou, S. L. Qiu, N. Su, J. Cong, L. Hou, Adv. Funct. Mater., 2024, 34, 2310155.
[56]	H. Z. Xu, Ke Ye, J. L. Yin, K. Zhu, J. Yan, G. L. Wang, D. X. Cao, J Power Sources, 2021, 491, 229592.

构建用于工业电流密度下高效电解尿素辅助制氢的Ni₂P/CoP界面催化剂

Construction of Ni₂P/CoP interface for highly efficient electrolysis of urea-assisted hydrogen production at industrial current densities

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 6

参考文献

相关文章 2

编辑推荐

Metrics

[1]	李家欣, 吕燕, 吴雪岩, 郭新玉, 杨卓君, 郭继玺, 周天华, 贾殿赠. 分级结构NiO纳米管/纳米片表面限域生长Pt亚纳米团簇催化剂用于尿素辅助节能产氢[J]. 催化学报, 2025, 69(2): 203-218.
[2]	段妍, 薛米风, 刘彬, 张曼, 王宇辰, 王宝俊, 章日光, 严凯. 理论和实验相结合研究NiCo₂O₄纳米片用于甘油电氧化反应机制[J]. 催化学报, 2024, 57(2): 68-79.