纳米高熵合金实现光催化剂肖特基势垒的调控用于光催化制氢与苯甲醇氧化耦合反应

doi:10.1016/S1872-2067(23)64492-4

催化学报 ›› 2023, Vol. 51: 90-100.DOI: 10.1016/S1872-2067(23)64492-4

纳米高熵合金实现光催化剂肖特基势垒的调控用于光催化制氢与苯甲醇氧化耦合反应

孙利娟^a^,^b, 王伟康^b, 路平^a, 刘芹芹^b^,^*(), 王乐乐^b, 唐华^a^,^*()

^a青岛大学环境科学与工程学院, 山东青岛266071
^b江苏大学材料科学与工程学院, 江苏镇江212013

收稿日期:2023-05-17 接受日期:2023-07-17 出版日期:2023-08-18 发布日期:2023-09-11
通讯作者: *电子信箱: huatang79@163.com (唐华), qqliu@ujs.edu.cn (刘芹芹).
基金资助:
国家自然科学基金(21975110);国家自然科学基金(21972058);山东省泰山青年学者计划

Enhanced photocatalytic hydrogen production and simultaneous benzyl alcohol oxidation by modulating the Schottky barrier with nano high-entropy alloys

Lijuan Sun^a^,^b, Weikang Wang^b, Ping Lu^a, Qinqin Liu^b^,^*(), Lele Wang^b, Hua Tang^a^,^*()

^aSchool of Environmental Science and Engineering, Qingdao University, Qingdao 266071, Shandong, China
^bSchool of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu, China

Received:2023-05-17 Accepted:2023-07-17 Online:2023-08-18 Published:2023-09-11
Contact: *E-mail: huatang79@163.com (H. Tang), qqliu@ujs.edu.cn (Q. Liu).
Supported by:
National Natural Science Foundation of China(21975110);National Natural Science Foundation of China(21972058);Taishan Youth Scholar Program of Shandong Province.

摘要/Abstract

摘要：

半导体表面修饰助催化剂可以降低界面反应势垒,提高界面反应速率.近期,含有至少五种主要元素且原子浓度为5%至35%的单相固溶体新型高熵合金(HEA)备受关注.与双金属或三金属纳米颗粒相比,HEA具有活性位点多、物理化学性质独特和热力学相对稳定等优势.理论研究表明,HEA的多种金属元素能够各自发挥作用,并在协同效应下展现出较好的催化性能.此外,HEA可以缩短活性位点之间的距离,增加吸附能,优化产物结构.尽管HEA应用前景广阔,但以其作为助催化剂同时进行氢气生产和增值精细化学合成的双功能光催化剂鲜有报道.
本文采用传统尿素热聚合法制备了g-C₃N₄纳米片,将其处理得到质子化的g-C₃N₄(HCN),同时采用低温油相合成法制备了直径为2nm的Pt₁₈Ni₂₆Fe₁₅Co₁₄Cu₂₇(HEA)纳米颗粒,并通过静电自组装方法,构筑了2D/0D HCN/HEA复合光催化剂.采用透射电子显微镜与原子力显微镜等方法对催化剂结构进行表征,结果表明,HEA纳米颗粒与质子化的g-C₃N₄纳米片紧密结合.紫外可见漫反射光谱、紫外光电子能谱以及电化学表征结果表明,HEA与HCN之间形成肖特基结,有效地加速电荷迁移并减少载流子的复合.原位表面光电压成像结果表明,光生电子从HCN纳米片通过肖特基结转移到HEA助催化剂.电化学线性扫描伏安法与阻抗测试表明,HEA极大地降低了HCN的产氢过电势,有效地促进了界面产氢速率,同时HEA的引入提高了HCN催化剂的电子传导速率.通过调控HEA与HCN的负载比例,复合光催化剂实现了高效的光催化产氢与苯甲醇选择性氧化为苯甲醛的耦合反应.其中,最佳样品光催化产氢速率达到2.4mmol g^‒1 h^‒1,苯甲醛产率达到5.44mmol g^‒1 h^‒1,分别是纯HCN的958倍和6.6倍.综上,本文为合理设计高性能光催化剂实现高效氧化还原偶联反应提供参考.

关键词: 高熵合金, 肖特基结, 光催化析氢, 苯甲醇氧化, 异质结

Abstract:

Catalysts play a vital role in photocatalytic water-splitting by converting solar energy into storable chemical energy. In this study, we successfully synthesized an HCN/HEA heterostructure by rationally combining the Pt₁₈Ni₂₆Fe₁₅Co₁₄Cu₂₇ nano-high-entropy alloy (HEA) as an effective cocatalyst with protonated g-C₃N₄ (HCN) nanosheets, via an electrostatic self-assembly method. The resulting HCN/HEA exhibited remarkable performance in both photocatalytic H₂ production and selective oxidation of benzyl alcohol to benzaldehyde. The integration of HEA into HCN leads to the formation of Schottky junctions, which can significantly accelerate charge migration and reduce the recombination of charge carriers. Further investigations using in situ surface photovoltage imaging demonstrated that the reducing cocatalyst HEA can act as a photogenerated electron trap. The best HCN/HEA heterojunction exhibited excellent photocatalytic hydrogen production activity, reaching 2.4 mmol g^-1 h^-1 and an impressive benzaldehyde production rate of 5.44 mmol g^-1 h^-1. These values were 958 and 6.6 times higher than those achieved with pristine HCN, respectively. This study offers promise for the rational design of high-performance cocatalysts to improve the transport, separation, and utilization of light-release charge carriers.

Key words: High-entropy alloy, Schottky junction, Photocatalytic H₂ evolution, Benzyl alcohol oxidation, Heterojunction

孙利娟, 王伟康, 路平, 刘芹芹, 王乐乐, 唐华. 纳米高熵合金实现光催化剂肖特基势垒的调控用于光催化制氢与苯甲醇氧化耦合反应[J]. 催化学报, 2023, 51: 90-100.

Lijuan Sun, Weikang Wang, Ping Lu, Qinqin Liu, Lele Wang, Hua Tang. Enhanced photocatalytic hydrogen production and simultaneous benzyl alcohol oxidation by modulating the Schottky barrier with nano high-entropy alloys[J]. Chinese Journal of Catalysis, 2023, 51: 90-100.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64492-4

https://www.cjcatal.com/CN/Y2023/V51/I8/90

图/表 8

Scheme 1. Schematic illustration for the synthesis procedure of HCN/HEA composites.

Fig. 1. (a,b) TEM images of HH-10. Inset shows the histogram of particle size distributions of HEA NPs. (c) HRTEM image of HH-10. AFM images of HCN (d) and HH-10 (e).

Fig. 2. XPS compositional analysis. Survey XPS spectra of HCN, HEA (a), and HH-10 (b) samples. High-resolution XPS spectra of Pt 4f (c), Fe 2p (d), Co 2p (e), Ni 2p (f), Cu 2p (g), C 1s (h), and N 1s (i).

Fig. 3. UPS spectra of the HCN (a), HH-10 (b), and HEA (c) samples. Possible photocatalytic mechanism of the HCN/HEA Schottky junction before contact (d), after contact (e), and under irradiation (f).

Fig. 4. (a) Comparison of photocatalytic activities of HCN, HEA, and HH-x samples in the photocatalytic conversion of 10% BA to H2 and BAD. (b) AQY of HH-10 sample. (c) Comparison of the photocatalytic conversion of BA to BAD and HER by different metal cocatalysts. (d) Cyclic stability of HH-5 composite sample. Reaction solution: 72 mL of water and 8 ml BA. LED light source: λ = 420 nm, 67.7 mW cm-2.

Fig. 5. Transient photocurrent response (a) and EIS (b) plots of HCN and HH-10 samples. Visible light-driven LSV curves (c) and Tafel slope (d) of HCN, HEA, and HH-10 samples. PL spectra (e) and TR-PL (f) decay spectra of HCN and HH-10 samples. Transient photocurrent density of HCN (g) and HH-10 (h) with/without adding H2O2. (i) SPV spectra of HCN and HH-10.

Fig. 6. AFM topography and KPFM image of the HH-10 sample in dark (a,b) and under 420 nm light illumination (c,d). (e) Height distribution of HEA NPs on HCN NSs surface. (f) Surface potential profiles under dark conditions and 420 nm light illumination (the quantitative values are all relative to the same calibrated probe).

Fig. 7. Proposed reaction mechanism for photooxidation-reduction catalyzed BA conversion coupled with H2 evolution over HCN/HEA heterostructure.

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纳米高熵合金实现光催化剂肖特基势垒的调控用于光催化制氢与苯甲醇氧化耦合反应

Enhanced photocatalytic hydrogen production and simultaneous benzyl alcohol oxidation by modulating the Schottky barrier with nano high-entropy alloys

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