通过钨对镍活性位点的电子改性实现苯甲胺选择性氧化耦合制氢

doi:10.1016/S1872-2067(23)64596-6

催化学报 ›› 2024, Vol. 58: 146-156.DOI: 10.1016/S1872-2067(23)64596-6

通过钨对镍活性位点的电子改性实现苯甲胺选择性氧化耦合制氢

屠振涛^a, 何晓洋^a, 刘璇^a, 熊登科^a, 左娟^b,*(), 吴德礼^c, 汪建营^a,*(), 陈作锋^a,*()

^a同济大学化学科学与工程学院, 上海200092
^b厦门理工学院材料科学与工程学院, 福建省功能材料与应用重点实验室, 福建厦门361005
^c同济大学环境科学与工程学院, 污染控制与资源化研究国家重点实验室, 上海200092

收稿日期:2023-11-11 接受日期:2024-01-06 出版日期:2024-03-18 发布日期:2024-03-28
通讯作者: *电子信箱: zuojuan@xmut.edu.cn (左娟),wang_jianying@tongji.edu.cn (汪建营),zfchen@tongji.edu.cn (陈作锋).
基金资助:
国家自然科学基金(22072107);国家自然科学基金(21872105);上海市自然科学基金(23ZR1464800);中央高校基本研究经费;上海市科学技术委员会(19DZ2271500)

Electronic modification of Ni active sites by W for selective benzylamine oxidation and concurrent hydrogen production

Zhentao Tu^a, Xiaoyang He^a, Xuan Liu^a, Dengke Xiong^a, Juan Zuo^b,*(), Deli Wu^c, Jianying Wang^a,*(), Zuofeng Chen^a,*()

^aSchool of Chemical Science and Engineering, Tongji University, Shanghai 200092, China
^bFujian Provincial Key Laboratory of Functional Materials and Applications, School of Materials Science and Engineering, Xiamen University of Technology, Xiamen 361005, Fujian, China
^cState Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science & Engineering, Tongji University, Shanghai 200092, China

Received:2023-11-11 Accepted:2024-01-06 Online:2024-03-18 Published:2024-03-28
Contact: *E-mail: zuojuan@xmut.edu.cn (J. Zuo),wang_jianying@tongji.edu.cn (J. Wang),zfchen@tongji.edu.cn (Z. Chen).
Supported by:
National Natural Science Foundation of China(22072107);National Natural Science Foundation of China(21872105);Natural Science Foundation of Shanghai Municipality(23ZR1464800);Fundamental Research Funds for the Central Universities and the Science & Technology Commission of Shanghai Municipality(19DZ2271500)

摘要/Abstract

摘要：

苯甲腈(BN)作为精细化学品、农用化学品和药品生产的重要中间体, 其制备受到研究人员的广泛关注. 传统的BN化学合成涉及有机物与氰化物之间的亲核取代反应. 然而, 由于氰化物等剧毒化学试剂的使用, 这一反应在实际应用中受到了一定的限制. 最近研究发现, 苯甲胺(BA)电化学氧化可为BN的生产提供一种清洁、高效、高选择性的方法. 此外, 与析氧反应(OER)相比, 苯甲胺氧化反应(BAOR)具有明显的热力学优势; 将BAOR与阴极析氢反应(HER)耦合, 可提高整体电解体系的能效和经济效益. 因此, 开发高效双功能电催化剂用于苯甲胺氧化及耦合析氢反应具有重要的基础研究意义和实际应用价值.

本文通过直接水热和高温磷化的方法, 在泡沫镍基底上负载了一种W-Ni₂P纳米片(W-Ni₂P/NF), 并探索了其作为双功能电催化剂在BAOR和HER的应用. 实验结果显示, 催化剂的纳米片结构不仅提供了充足的活性位点, 还有助于离子传输. 钨的掺杂显著增强了电化学传导性, 改善了水吸附性, 并优化了氢吸附能, 进而提升了催化剂的HER性能. 此外, 钨的引入促进了电子从镍向钨的转移, 形成了缺电子的镍区域; 在W-Ni₂P催化的BAOR过程中, 缺电子的镍活性位点与供电子的氨基(-NH₂)相互作用, 有效促进了氨基的吸附和活化, 进一步推动了脱氢反应和C≡N键的形成. 电化学测试结果表明, 在1 mol L^‒1 KOH溶液中, W-Ni₂P催化剂发生HER的过电位为80 mV (10 mA cm^-2), 其性能可与商业Pt/C电极相媲美. 在含有25 mmol L^‒1 BA的1 mol L^‒1 KOH溶液中, 仅需施加1.42 V电位, W-Ni₂P催化剂即可达到100 mA cm^-2的氧化电流密度, 这比OER所需电位低350 mV. 此外, 当组装W-Ni₂P/NF||W-Ni₂P/NF电解槽时, 在1 mol L^‒1 KOH和25 mmol L^‒1 BA的电解液中, 仅需1.41 V的电解电压即可达到10 mA cm^-2的电流密度, 实现了阴极制氢和阳极增值BN的同时生产, 且反应的法拉第效率达到95%. 采用电化学原位拉曼光谱和红外光谱研究了反应的活性位点和关键中间产物. 结合密度泛函理论计算, 阐明了BAOR的催化机理以及反应路径, 深入分析了W掺杂在优化吸附能和提高W-Ni₂P电催化剂催化活性方面的优化作用.

综上所述, 本文成功制备了高活性、高稳定性的钨掺杂磷化镍纳米片双功能催化剂, 并将其应用于两电极电解体系中, 实现了阴、阳极高附加值产物(苯甲腈和氢气)的同时生成. 本研究为电化学合成高价值腈化合物和制氢先进催化剂的设计、制备提供了一定的参考和借鉴.

关键词: 双功能电催化剂, 选择性氧化, 苯甲腈电合成, 脱氢作用, 析氢反应

Abstract:

We present self-supporting W-doped Ni₂P nanosheet arrays, serving as bifunctional catalysts for selective electrooxidation of benzylamine (BA) to high-value benzonitrile (BN), while simultaneously promoting hydrogen production. The assembled W-Ni₂P/NF||W-Ni₂P/NF (NF: nickel foam) electrolyzer requires a voltage of only 1.41 V to achieve a current density of 10 mA cm^‒2 in alkaline solution containing 25 mmol L^‒1 BA, exhibiting an impressive Faradaic efficiency 95% for benzonitrile synthesis. In-situ Raman and FTIR spectroscopies identify catalytically active NiOOH centers and key catalytic intermediates. X-ray absorption spectroscopy (XAS) and theoretical calculations suggest that W acts as electron attractors on adjacent Ni atoms, forming an electron-deficient Ni domain that promotes the adsorption and activation of -NH₂ group, leading to efficient dehydrogenation into C≡N bonds. The doped W also optimizes the adsorption of hydrogen (ΔG_H*) on Ni₂P, thus promote the hydrogen evolution. This work highlights the electronic modification of Ni active sites as a key factor for bifunctional electrocatalysis in selective nitrile electrosynthesis and concurrent hydrogen evolution.

Key words: Bifunctional electrocatalyst, Selective oxidation, Benzonitrile electrosynthesis, Dehydrogenation, Hydrogen evolution reaction

屠振涛, 何晓洋, 刘璇, 熊登科, 左娟, 吴德礼, 汪建营, 陈作锋. 通过钨对镍活性位点的电子改性实现苯甲胺选择性氧化耦合制氢[J]. 催化学报, 2024, 58: 146-156.

Zhentao Tu, Xiaoyang He, Xuan Liu, Dengke Xiong, Juan Zuo, Deli Wu, Jianying Wang, Zuofeng Chen. Electronic modification of Ni active sites by W for selective benzylamine oxidation and concurrent hydrogen production[J]. Chinese Journal of Catalysis, 2024, 58: 146-156.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64596-6

https://www.cjcatal.com/CN/Y2024/V58/I3/146

图/表 9

Scheme 1. Illustration of the current industrial route for benzonitrile synthesis and their wide applications.

Scheme 2. Schematic illustration for synthesis of bifunctional W-Ni2P/NF nanoarray electrocatalysts and selective oxidation of benzylamine.

Fig. 1. SEM images of Ni2P (a,b) and W-Ni2P (c,d) at low and high magnifications. TEM (e) and HRTEM (f) images of W-Ni2P. (g) Elemental mapping images of Ni, P and W on W-Ni2P.

Fig. 2. (a) XRD patterns of W-Ni2P and Ni2P. XPS spectra for W 4f (b), P 2p (c), and Ni 2p (d). Ni K-edge XANES spectra (e) and R space Fourier transform EXAFS spectra (f) of Ni foil, NiO, Ni2P, and W-Ni2P. (g) Wavelet transform plots of Ni foil, NiO, Ni2P, and W-Ni2P.

Fig. 3. HER polarization curves (a) and Tafel plots (b) for various catalysts in 1.0 mol L?1 KOH solution. (c) Nyquist plots of various catalysts at an overpotential of 110 mV; the inset shows the equivalent circuit diagram. (d) CV curves for W-Ni2P at scan rates from 20 to 120 mV s-1. (e) Cdl values of various catalysts. (f) j-t curve of W-Ni2P and LSV curves before and after 3000 CV scan cycles.

Fig. 4. (a) LSV curves of W-Ni2P in 1.0 mol L?1 KOH with and without 25 mmol L?1 BA. (b) Potential comparison of BAOR and OER at different current densities. LSV curves (c) and Tafel plots (d) for W-Ni2P, Ni2P, W-Ni LDH, Ni LDH and RuO2 in 1.0 mol L?1 KOH containing 25 mmol L?1 BA. (e) 1H NMR spectra for BA and its oxidation products during electrolysis. (f) 1H NMR local magnification from 7.0 to 8 δ. (g) 13C NMR spectra for BA and its oxidation products during electrolysis. (h) Nyquist plots of various catalysts at an overpotential of 110 mV; the inset shows the equivalent circuit diagram. (i) j-t curve (inset) of W-Ni2P and LSV curves before and after stability test.

Fig. 5. Potential dependent, in-situ Raman spectra at W-Ni2P in 1.0 mol L?1 KOH without (a) and with (b) 25 mmol L?1 BA. (c) In-situ Raman spectra at 1.45 V after addition of 25 mmol L?1 BA. (d) In-situ FTIR spectra of W-Ni2P at different applied potentials for the BAOR. (e) In-situ FTIR spectra of W-Ni2P at different times following (d) at the open circuit potential.

Fig. 6. (a) Schematic diagram of a two-electrode electrolyzer with W-Ni2P as the anode and cathode. Polarization curves (b) and comparison of cell voltages (c) for different current densities achieved at W-Ni2P electrodes in 1.0 mol L-1 KOH with and without 25 mmol L-1 BA. (d) Chronopotentiometric curves of BA oxidation at W-Ni2P at 20 mA cm-2 in 1.0 mol L-1 KOH containing 25 mmol L-1 BA; the inset illustrates the change in voltage before and after electrolysis. (e) Optical photo of a HER||BAOR electrolytic cell powered by a small solar cell.

Fig. 7. Theoretical models of W-Ni2P (a), Ni2P (b), W-Ni2P@W-NiOOH (c) and Ni2P@NiOOH (d). (e) The free energy diagram of HER on the W-Ni2P and Ni2P. (f) The partial density of states (PDOS) of W-Ni2P and Ni2P. (g) Benzylamine adsorption energy on W-Ni2P@W-NiOOH and Ni2P@NiOOH. (h) Electron density difference at the W-Ni2P@W-NiOOH interface. (i) The free energy diagram of BAOR on the W-Ni2P and Ni2P.

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通过钨对镍活性位点的电子改性实现苯甲胺选择性氧化耦合制氢

Electronic modification of Ni active sites by W for selective benzylamine oxidation and concurrent hydrogen production

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