异质结构NiSe2/MoSe2用于高效尿素辅助电解水制氢

doi:10.1016/S1872-2067(23)64490-0

摘要/Abstract

摘要：

电催化水分解是实现绿色制氢的理想方法之一.然而,阳极析氧反应(OER)固有的缓慢动力学和高理论电压(1.23V),使得电解水制氢的能效受到严重限制.采用理论电位更低和热力学更有利的小分子氧化反应替代OER过程,可以在降低电能耗的同时降解污染物或生成有附加值的产物,能够带来多重效益.尿素氧化反应(UOR)具有较低的理论电压(0.37V),是替代OER的潜在反应之一.然而,UOR中复杂的六电子转移严重阻碍了尿素电解的整体效率.因此,设计经济且高效的电催化剂来促进UOR固有的缓慢动力学过程非常必要.硒化镍具有电子构型多样和结构调控灵活等优点,被认为是有效的UOR催化剂.然而,UOR过程涉及催化剂表面多种反应中间体的吸附/解吸,单相催化剂要同时满足多种反应中间的吸附/解吸是一项艰巨的挑战.众所周知,非均相电催化涉及电子转移以及电催化剂表面反应物和产物的吸附和解吸.因此,催化剂的电催化性能在很大程度上取决于材料表面的电子特性.通过构建异质结构是一种有效策略,可以调节电催化剂的电子结构,优化反应中间体的化学吸附行为,实现不同组份高效协同电催化.研究表明,通过界面工程优化结构和电子特性可进一步促进UOR的动力学.MoSe₂具有良好的稳定性和导电性,与镍基催化剂组合构建异质结构能够改善电催化反应中的催化动力学.
本文通过简单的水热和低温硒化方法构建了异质NiSe₂/MoSe₂微球作为UOR的电催化剂.差分电荷密度和Mulliken电荷分析结果表明,MoSe₂与NiSe₂的耦合引起界面处的电荷重新分布,促使电子从NiSe₂向MoSe₂转移,更容易形成高价态Ni(NiOOH)活性物种.另外,异质界面的构建优化了催化剂表面的电子结构并调节d带中心,改变反应途径,降低反应能垒,从而提高UOR的反应活性.异质结NiSe₂/MoSe₂微球由于其独特的结构特征、强的协同耦合作用、增加的活性中心和高含量的高价Ni³⁺物种的综合优势而具有高效的催化性能.当负载在玻碳电极上时,仅需1.33V的电压就能驱动10mA cm^-2的电流密度,该活性优于大多数已报道的非贵金属UOR催化剂.将NiSe₂/MoSe₂催化剂组装到UOR//HER电解槽中时,NiSe₂/MoSe₂||Pt/C具有较低的操作电压和长期稳定性,在1.47V的电池电压下电流密度达到10mA cm^-2,比单纯的水电解降低了约220mV.与OER相比,热力学上有利的UOR可以作为阳极OER替代反应.综上,本文为能源/环境相关的催化反应提供了一个有效的催化剂体系,对构建高效异质结催化系统具有借鉴意义.

关键词: 电解水, 尿素氧化, 催化剂, 硒化镍, 硒化钼

Abstract:

Efficient heterogeneous catalysts play a very important role in the value-updated green hydrogen production from urea-containing wastewater. Herein, NiSe₂/MoSe₂ heterostructured catalyst with optimized interfacial electron redistribution and urea adsorption energies via a strong built-in electric field was demonstrated effective for the urea-assisted water splitting reactions. Efficient catalytic performance was found on NiSe₂/MoSe₂ hybrid microsphere owing to the combined merits such as the unique structure features, the strong synergetic coupling effects, the increased active sites, and the high amount of intrinsic Ni³⁺ species. Excellent urea oxidation activity was found to drive 10 mA cm^‒2 at the potential of 1.33 V when loaded on the glassy carbon electrode, and a cell voltage of 1.47 V was required in the NiSe₂/MoSe₂||Pt/C urea-water electrolyzer to drive 10 mA cm^‒2, about 220 mV less than that of water electrolysis, indicating a less energy consumption technique during the electrolysis. The spectroscopic and theoretical analysis revealed the effective synergy of the Ni-Se bond and Mo-Se bond that would be promising for efficient catalyst system construction.

Key words: Water electrolysis, Urea oxidation, Heterostructured catalyst, NiSe₂, MoSe₂

尹春, 杨甫林, 王书莉, 冯立纲. 异质结构NiSe₂/MoSe₂用于高效尿素辅助电解水制氢[J]. 催化学报, 2023, 51: 225-236.

Chun Yin, Fulin Yang, Shuli Wang, Ligang Feng. Heterostructured NiSe₂/MoSe₂ electronic modulation for efficient electrocatalysis in urea assisted water splitting reaction[J]. Chinese Journal of Catalysis, 2023, 51: 225-236.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64490-0

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图/表 5

Fig. 1. XRD patterns (a), TDOS (b), and PDOS (c) of NiSe2/MoSe2, NiSe2, and MoSe2 catalysts. (d) Electron density difference for NiSe2/MoSe2 (yellow: electron depletion and blue: electron accumulation). (e) Total electronic values of Mulliken for NiSe2/MoSe2 and NiSe2. (f) Adsorption energy of urea molecules on the surface of catalysts. XPS spectra of Ni 2p (g), Mo 3d (h), Se 3d (i) of catalysts.

Fig. 2. (a) SEM image of NiSe2/MoSe2. (b,c) TEM images of NiSe2/MoSe2. The high resolution TEM image (d), SAED pattern (e), energy dispersive X-ray spectroscopy (f), STEM (g) and elemental mapping images (g?l) of NiSe2/MoSe2.

Fig. 3. The LSV curves (a) and Tafel plots (b) for the NiSe2/MoSe2, NiSe2, MoSe2, and IrO2 samples. (c) Nyquist plots of NiSe2/MoSe2, NiSe2, and MoSe2 catalysts at 1.54 V. Inset: the equivalent circuit model for electrochemical impedance spectrum. (d) Scan-rate dependence of the current densities derived from double-layer capacitance measurements. (e) The LSV curves of NiSe2/MoSe2 before and after 1000 CV cycles stability test. Inset for the CA curves recorded at 1.54 V of NiSe2/MoSe2 for 10 h. (f) Specific activity polarization curves of NiSe2/MoSe2, NiSe2, and MoSe2.

Fig. 4. CV curves measured in 1 mol L?1 KOH solution (a) and in 1 mol L?1 KOH solution with 0.33 mol L?1 urea (b) for NiSe2/MoSe2, NiSe2, and MoSe2 catalysts at 10 mV s?1. (c) The corresponding Tafel slope of these catalysts. (d) Nyquist plots and fitting curves at 1.36 V. Inset: the equivalent circuit model for electrochemical impedance spectrum. (e) CA curves for urea oxidation at 1.39 V. (f) LSV curve of the water and urea electrolysis of NiSe2/MoSe2||Pt/C. Inset: Time-dependent current density curve for 10 h. (g) Free energy diagram of NiSe2 (210) and NiSe2 (210)/MoSe2 (100) for UOR.

Fig. 5. Morphology observed by TEM for NiSe2/MoSe2 after stability test. (a,b) TEM images. (c) HR-TEM image. (d) SAED pattern. (e) EDS pattern. (f?k) STEM and elemental mapping images. The XPS spectra comparison for NiSe2/MoSe2 catalyst before and after stability test: Ni 2p (l), Mo 3d (m), Se 3d (n).

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异质结构NiSe₂/MoSe₂用于高效尿素辅助电解水制氢

Heterostructured NiSe₂/MoSe₂ electronic modulation for efficient electrocatalysis in urea assisted water splitting reaction

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