肖特基结与金属尺寸效应协同增强光催化硝酸还原

doi:10.1016/S1872-2067(24)60280-9

催化学报 ›› 2025, Vol. 73: 358-367.DOI: 10.1016/S1872-2067(24)60280-9

肖特基结与金属尺寸效应协同增强光催化硝酸还原

孙雪萌^a^,¹, 刘佳男^a^,¹, 李琪^c, 汪成^a^,^b(), 蒋保江^a()

^a黑龙江大学功能无机材料化学教育部重点实验室, 黑龙江哈尔滨 150080
^b广东省化学与精细化工实验室揭阳中心, 广东揭阳 515200
^c哈尔滨工程大学材料科学与化学工程学院, 黑龙江哈尔滨 150001

收稿日期:2025-01-02 接受日期:2025-02-11 出版日期:2025-06-18 发布日期:2025-06-12
通讯作者: *电子信箱: wangc_93@gdut.edu.cn (汪成),jbj@hlju.edu.cn (蒋保江).
作者简介:¹共同第一作者.
基金资助:
国家自然科学基金(U24A20550);国家自然科学基金(52273264);黑龙江省自然科学基金重点项目(ZD2024B001)

Schottky junction coupling with metal size effect for the enhancement of photocatalytic nitrate reduction

Xuemeng Sun^a^,¹, Jianan Liu^a^,¹, Qi Li^c, Cheng Wang^a^,^b(), Baojiang Jiang^a()

^aKey Laboratory of Functional Inorganic Material Chemistry, Ministry of Education of the People’s Republic of China, Heilongjiang University, Harbin 150080, Heilongjiang, China
^bGuangdong Provincial Laboratory of Chemistry and Fine Chemical Engineering Jieyang Center, Jieyang 515200, Guangdong, China
^cCollege of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, Heilongjiang, China

Received:2025-01-02 Accepted:2025-02-11 Online:2025-06-18 Published:2025-06-12
Contact: *E-mail: wangc_93@gdut.edu.cn (C. Wang),jbj@hlju.edu.cn (B. Jiang).
About author:¹Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(U24A20550);National Natural Science Foundation of China(52273264);Key Project of the Heilongjiang Provincial Natural Science Foundation(ZD2024B001)

摘要/Abstract

摘要：

地表水和地下水中硝酸盐的存在是一个普遍的问题, 主要归因于化肥、工业化学品的使用及相关活动. 这些因素对环境和人类健康都产生了重大有害影响. 硝酸盐污染严重威胁生态系统平衡, 光催化硝酸盐还原(PcNR)因其环境效益和高效而受到广泛关注. 然而, 光催化活性往往受到硝酸盐的强结合、动力学惰性以及光催化硝酸盐还原中的多电子和多光子过程的限制. 因此, 开发一种有效的PcNR工艺仍然是一项紧迫而艰巨的挑战. 其中, 肖特基结(Schottky)的构建显示出巨大的实际应用潜力. 在金属助催化剂和半导体之间形成的肖特基结, 通过克服激发时的肖特基势垒, 促进了光电子向费米能级较低的贵金属表面转移. 肖特基势垒有效地阻止了光生电子的反向流动, 从而抑制了光生电荷的复合. 然而, 肖特基结内金属尺寸对光催化硝酸盐还原的影响尚不清楚. 在特定范围内, 金属纳米颗粒(NPs)的尺寸对催化活性至关重要: 较小的NPs表现出更多的局域电子态, 而较大的颗粒, 与载流子接触的金属表面积减少, 提供的电荷转移界面位点减少, 从而降低了电荷转移效率, 减弱了载流子对金属NPs的影响. COFs是由共价键形成的新型多孔材料. 通过选择不同的单体和合成条件, COFs可以被设计成具有特定的孔径、表面积和适合各种催化反应的官能团. 然而, 大多数COFs表现出相对较低的导电性, 这限制了光生载流子的迁移和分离, 从而降低了整体光催化性能. 在光催化过程中, Au通常比其他贵金属(如Pt、Pd和Ag)表现出更高的催化活性, 从而能够有效利用阳光, 并在低能耗条件下促进反应. 因此, 研究Au的尺寸效应及其与COF载体的相互作用对于开发高效的硝酸还原光催化体系至关重要.

采用溶剂热法, 以1,3,5-三(4-氨基苯基)苯(TAPB)和均苯三甲醛(BTCA)为原料, 在140 °C下进行热聚合, 反应10 h, 得到具有类红细胞形貌的TAPB-BTCA-COF材料. 傅里叶变换红外光谱和固体核磁共振等结果证明了COF的成功合成. 随后通过控制光强来制备出不同尺寸Au纳米颗粒(Au NPs)的Au-COF材料. 结合X射线衍射、扫描电子显微镜和透射电子显微镜表征结果表明, 不同尺寸Au NPs的Au-COF催化剂的成功制备以及Au NPs附着在COF表面. 紫外-可见漫反射光谱结果表明, Au-COF材料相比于单独COF扩大了可见光吸收范围. 在不添加任何牺牲剂和光敏剂的情况下, Au₂-COF复合材料具有最高的硝酸盐还原性能, 达到382.48 μmol g^-1 h^-1, 是纯COF (67.25 μmol g^-1 h^-1)的5.7倍. 通过原位X射线光电子能谱结合理论计算功函数推断出Au₂-COF复合材料内部载流子转移的机理, 证明了Au与COF之间肖特基结的形成, 肖特基势垒有效地阻止了被Au捕获的光生电子的反向转移, 在Au₂-COF复合材料中提供了从COF到Au的单向电子转移途径. 这种从COF到Au的单向电子转移途径有效地提高了Au₂-COF复合材料的电荷分离效率, 这是其具有高光催化活性的关键. 光电流响应、电化学阻抗谱、稳态荧光和瞬态荧光结果表明, 小尺寸Au₂-COF催化剂形成的肖特基结改善了光生电子-空穴对的分离, 提高了载流子迁移效率, 从而促进了光催化反应. 使用原位红外光谱实时监测了光催化硝酸盐还原整个反应过程中各种中间体和产物, 实验结果证明了将NO₃^-还原为NH₄⁺的可行性.

综上所述, 通过合成不同Au NPs尺寸的Au-COF肖特基结催化剂, 研究了金属尺寸对光催化硝酸还原性能的影响. 本研究阐明了金属尺寸对肖特基结在光催化硝酸盐活性中的影响, 为设计高活性的硝酸还原光催化剂提供了有价值的见解.

关键词: 肖特基结, 硝酸盐还原, 光催化, 共价有机框架

Abstract:

Nitrate pollution poses a significant environmental challenge, and photocatalytic nitrate reduction has garnered considerable attention due to its efficiency and environmental advantages. Among these, the development of Schottky junctions shows considerable potential for practical applications. However, the impact of metal nanoparticle size within Schottky junctions on photocatalytic nitrate reduction remains largely unexplored. In this study, we propose a novel method to modulate metal nanoparticle size within Schottky junctions by controlling light intensity during the photodeposition process. Smaller Au nanoparticles were found to enhance electron accumulation at active sites by promoting charge transfer from COF to Au, thereby improving internal electron transport. Additionally, the Schottky barrier effectively suppressed reverse electron transfer while enhancing NO₃^- adsorption and activation. The Au₂-COF exhibited remarkable nitrate reduction performance, achieving an ammonia yield of 382.48 μmol g^-1 h^-1, 5.7 times higher than that of pure COF. This work provides novel theoretical and practical insights into using controlled light intensity to regulate metal nanoparticle size within Schottky junctions, thereby enhancing photocatalytic nitrate reduction.

Key words: Schottky junction, Nitrate reduction, Photocatalysis, Covalent organic frameworks

孙雪萌, 刘佳男, 李琪, 汪成, 蒋保江. 肖特基结与金属尺寸效应协同增强光催化硝酸还原[J]. 催化学报, 2025, 73: 358-367.

Xuemeng Sun, Jianan Liu, Qi Li, Cheng Wang, Baojiang Jiang. Schottky junction coupling with metal size effect for the enhancement of photocatalytic nitrate reduction[J]. Chinese Journal of Catalysis, 2025, 73: 358-367.

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图/表 7

Scheme 1. Synthesis process of Au2-COF composites.

Fig. 1. (a) FT-IR spectra of COF. (b) The solid-state 13C NMR spectra of COF. (c) Experimental and simulated PXRD patterns of COF. (d) XRD images of COF, Au25-COF and Au2-COF.

Fig. 2. (a, b) SEM and TEM images of COF. (c, d) TEM and HRTEM images of Au2-COF. (e) Element mapping images of C, N and Au.

Fig. 3. (a-c) In-situ XPS spectra of C 1s (a), N 1s (b), and Au 4f (c) of samples. (d,e) Work functions of COF and Au. (f) Electron density difference of Au2-COF. (g-i) The charge transfer mechanism at the Au2-COF Schottky junction interface (Evac: Vacuum level, Ef, m: Metal Fermi level, Ef, s: Semiconductor Fermi level, EC: Conduction band level, EV: Valence band level, φ: Work function.).

Fig. 4. Transient photocurrent responses (a) and EIS Nyquist plots (b) of COF, Au25-COF and Au2-COF. Steady-state PL (c) and TRPL (d) spectra of COF, Au25-COF and Au2-COF.

Fig. 5. NH4+ yield (a) and NH4+ formation rate (b) of COF, Au25-COF and Au2-COF. (c) Comparison of photocatalytic nitrate reduction rates of Au2-COF and other catalyst. (d) NH4+ field of Au2-COF at different NO3- concentrations. (e) 1H NMR spectra of time-dependent concentration change of NH4+ using 15NO3- and 14NO3- as the NO3- source. (f) AQE of Au2-COF.

Fig. 6. (a) In-situ DRIFTS spectra from the as-prepared Au2-COF during the photocatalytic nitrate reduction. (b) Possible mechanism of photocatalytic nitrate reduction process in Au2-COF.

参考文献

[1]	W. Yang, J. Wang, R. Chen, L. Xiao, S. Shen, J. Li, F. Dong, J. Mater. Chem. A, 2022, 10, 17357-17376.
[2]	Z. Wang, G. Chen, X. Wang, G. Yang, Y. Liu, C. Zhang, J. Hazard. Mater., 2021, 401, 123378.
[3]	Y. Wang, H. Yin, X. Zhao, Y. Qu, A. Zheng, H. Zhou, W. Fang, J. Li, Appl. Catal. B, 2024, 341, 123266.
[4]	F. Hu, J. Ye, J. Zhang, W. Zhang, P. Chen, Z. Yuan, Z. Xu, J. Hazard. Mater., 2024, 479, 135605.
[5]	X. Li, J. Chang, H. Zhang, J. Feng, J. Ma, C. Bai, Y. Ren, J. Hazard. Mater., 2024, 462, 132683.
[6]	Y. Zhang, Z. Ma, S. Yang, Q. Wang, L. Liu, Y. Bai, D. Rao, G. Wang, H. Li, X. Zheng, Sci. Bull., 2024, 69, 1100-1108.
[7]	L. Zhang, R. Li, L. Guo, L. Cui, X. Zhang, Y. Wang, Y. Wang, X. Jian, X. Gao, C. Fan, J. Wang, J. Liu, ACS Catal., 2024, 14, 5696-5709.
[8]	J. E. Silveira, A. R. Ribeiro, J. Carbajo, G. Pliego, J. A. Zazo, J. A. Casas, Water Res., 2021, 200, 117250.
[9]	P. Li, B. Zhang, ACS Catal., 2024, 14, 18345-18353.
[10]	X. Huang, K. Wu, F. Yang, R. Fu, Y. Ji, W. Kong, C. Su, B. Xiao, Chem. Eng. J., 2025, 504, 158995.
[11]	Q. Ye, Y. Zhou, Y. Xu, Q. Zhang, X. Shi, D. Li, D. Tian, D. Jiang, Chem. Eng. J., 2023, 463, 142395.
[12]	X.-Q. Qiao, C. Li, W. Chen, H. Guo, D. Hou, B. Sun, Q. Han, C. Sun, D.-S. Li, Chem. Eng. J., 2024, 490, 151822.
[13]	X. Jiang, S. Sun, Y. Wang, L. Zhao, F. Huang, S. Li, J. Mater. Chem. A, 2024, 12, 12146-12154.
[14]	M. Gao, F. Tian, X. Zhang, Y. Liu, Z. Chen, Y. Yu, W. Yang, Y. Hou, Nano Energy, 2022, 103, 107767.
[15]	H. Li, H. Wang, L. Li, X. Ma, Y. Li, Z. Jin, Sep. Purif. Technol., 2025, 362, 131615.
[16]	Y. Bi, Y. Fang, L. Yuan, J. Li, C. Zhang, P. Shan, X. Zhang, C. Liu, C. Yu, ACS Catal., 2025, 15, 246-254247.
[17]	C. Ruan, K. Gao, Q. Wang, S. Luo, Y. Zhang, M. Yang, S. Zhong, Q. Wu, Y. Tian, Z. Zhang, Sep. Purif. Technol., 2025, 362, 131723.
[18]	H. Ran, Q. Xu, Y. Yang, H. Li, J. Fan, G. Liu, L. Zhang, J. Zou, H. Jin, S. Wang, ACS Catal., 2024, 14, 11675-11704.
[19]	L. Ye, Z. Xia, Q. Xu, Y. Yang, X. Xu, H. Jin, S. Wang, Chem. Commun., 2023, 59, 9872-9875.
[20]	W. Yang, J. Zhang, Q. Xu, Y. Yang, L. Zhang, Acta Phys.-Chim. Sin., 2024, 40, 2312014.
[21]	Zhang , X. Li, X. Dong, H. Hao, X. Lang, Chin. J. Catal., 2022, 43, 2395-2404.
[22]	J. Li, Z. Zhang, J. Jia, X. Liu, Chem. Res. Chin. Univ., 2022, 38, 275-289.
[23]	X. Lang, a X. Chen, J. Zhao, Chem. Soc. Rev., 2014, 43, 473-486.
[24]	X. Sun, J. Liu, H. Wang, Q. Li, J. Zhou, P. Li, K. Hu, C. Wang, B. Jiang, Chem. Eng. J., 2023, 472, 144750.
[25]	X. Yang, L. Ren, D. Jiang, L. Yin, Z. Li, Y. Yuan, Small, 2024, 20, 2308408.
[26]	Z. X. Sun, K. Sun, M. L. Gao, Ö. Metin, H. L. Jiang, Angew. Chem. Int. Ed., 2022, 61, e202206108.
[27]	Q. Shang, Y. Liu, J. Ai, Y. Yan, X. Yang, D. Wang, G. Liao, J. Mater. Chem. A, 2023, 11, 21109-21122.
[28]	T. He, Z. Zhao, R. Liu, X. Liu, B. Ni, Y. Wei, Y. Wu, W. Yuan, H. Peng, Z. Jiang, Y. Zhao, J. Am. Chem. Soc., 2023, 145, 6057-6066.
[29]	Y. Deng, Z. Zhang, P. Du, X. Ning, Y. Wang, D. Zhang, J. Liu, S. Zhang, X. Lu, Angew. Chem. Int. Ed., 2020, 59, 6082-6089.
[30]	Z. Zhou, C. Bie, P. Li, B. Tan, Y. Shen, Chin. J. Catal., 2022, 43, 2699-2707.
[31]	E. M. Sabio, R. L. Chamousis, N. D. Browning, F. E. Osterloh, J. Phys. Chem. C, 2012, 116, 3161-3170.
[32]	A. Chakraborty, A. Alam, U. Pal, A. Sinha, S. Das, T. Saha-Dasgupta, P. Pachfule, Nat. Commun., 2025, 16, 503.
[33]	H. Jiang, C. Cao, W. Liu, H. Zhang, Q. Li, S. Zhu, X. Li, J. Li, J. Chang, W. Hu, Z. Xing, X. Zou, G. Zhu, J. Energy Chem., 2025, 104, 127-135.
[34]	Q. Yang, Q. Xu, S. H. Yu, H. L. Jiang, Angew. Chem. Int. Ed., 2016, 55, 3685-3689.
[35]	M. Guo, X. Guan, Q. Meng, M. L. Gao, Q. Li, H. L. Jiang, Angew. Chem. Int. Ed., 2024, 63, e202410097.
[36]	G. Xia, Y. Meng, Q. Fu, Z. Huang, B. Xie, Z. Ni, S. Xia, Chem. Eng. J., 2024, 498, 155849.
[37]	C. Qin, Y. Yang, G. Zhou, E.H. Ang, H. Wang, Y. Wu, Chem. Eng. J., 2024, 487, 150571.
[38]	Z. Xiao, H. Do, A. Yusuf, H. Jia, H. Ma, S. Jiang, J. Li, Y. Sun, C. Wang, Y. Ren, G. Z. Chen, J. He, J. Hazard. Mater., 2024, 462, 132744.
[39]	W. Deng, X. Hao, J. Yang, Z. Jin, Appl. Catal. B, 2025, 360, 124551.
[40]	M. Zhang, Y. Zhang, L. Tang, Y. Zhu, J. Wang, C. Feng, S. Fu, L. Qiao, Y. Zhang,, Appl. Catal. B, 2021, 295, 120278.
[41]	J. Cao, B. Luo, Y. Zhang, J. Li, L. Ma, D. Jing, Sep. Purif. Technol., 2023, 327, 124965.
[42]	C. C. Chang, Y. C. Chen, K. C. Wu, H. N. Priyadarshini, L. Y. Lee, J. L. Chen, C. R. Lee, C. W. Pao, D. Y. Wang, ChemCatChem, 2024, 16, e202400596
[43]	H. Kominami, T. Nakaseko, Y. Shimada, A. Furusho, H. Inoue, S.-y. Murakami, Y. Kera, B. Ohtani, Chem. Commun., 2005, 2933-2935.
[44]	N. Tong, Y. Wang, Y. Liu, M. Li, Z. Zhang, H. Huang, T. Sun, J. Yang, F. Li, X. Wang, J. Catal., 2018, 361, 303-312.
[45]	I. Hong, H. S. Moon, B. J. Park, Y.-A. Chen, Y.-P. Chang, B. Song, D. Lee, Y. Yun, Y.-J. Hsu, J. W. Han, K. Yong, Chem. Eng. J., 2024, 484, 149506.
[46]	H. S. Moon, B. Song, J. Jeon, T.-H. Lai, Y.-P. Chang, Y.-D. Lin, J. K. Park, Y.-G. Lin, Y.-J. Hsu, H. Shin, Y. Yun, K. Yong, Appl. Catal. B, 2023, 339, 123185.
[47]	H. Peng, Y. Liu, Y. Wang, M. Song, H. Song, P. Chen, S.-F. Yin, ACS Catal., 2024, 14, 2971-2980.
[48]	K. Cheng, S. Li, Q. Cheng, L. Zhang, Y. Jiang, F. Li, H. Ma, D. Zhang, Adv. Funct. Mater., 2024, 2417914.
[49]	H. Li, S. Xue, F. Cao, C. Gao, Q. Wei, R. Li, A. Zhou, S. Wang, X. Yue, Chemosphere, 2023, 325, 138336.
[50]	Z. Liu, S. Fan, X. Li, Z. Niu, J. Wang, C. Bai, J. Duan, M. O. Tadé, S. Liu, Appl. Catal. B, 2023, 327, 122416.
[51]	H.-T. Ren, S.-Y. Jia, J.-J. Zou, S.-H. Wu, X. Han, Appl. Catal. B, 2015, 176-177, 53-61.
[52]	N. Zhang, A. Jalil, D. Wu, S. Chen, Y. Liu, C. Gao, W. Ye, Z. Qi, H. Ju, C. Wang, X. Wu, L. Song, J. Zhu, Y. Xiong, J. Am. Chem. Soc., 2018, 140, 9434-9443.
[53]	J. Li, R. Chen, J. Wang, Y. Zhou, G. Yang, F. Dong, Nat. Commun., 2022, 13, 1098.
[54]	Y. Xi, Y. Xiang, T. Bao, Z. Li, C. Zhang, L. Yuan, J. Li, Y. Bi, C. Yu, C. Liu, Angew. Chem. Int. Ed., 2024, 63, e202409163.
[55]	X. Sun, J. Liu, R. Yang, H. Gu, B. Chen, C. Wang, B. Jiang, J. Colloid Interface Sci., 2025, 678, 67-75.
[56]	J. Liu, X. Sun, Y. Fan, Y. Yu, Q. Li, J. Zhou, H. Gu, K. Shi, B. Jiang, Small, 2024, 20, 2306344.
[57]	H. Wang, J. Fan, J. Zou, Y. Zheng, D. Wang, J. Jiang, J. Mater. Chem. A, 2024, 12, 30429-30441.

肖特基结与金属尺寸效应协同增强光催化硝酸还原

Schottky junction coupling with metal size effect for the enhancement of photocatalytic nitrate reduction

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