Co(II)-空穴和Pt-电子助催化剂协同作用增强P掺杂g-C3N4光催化产氢性能

doi:10.1016/S1872-2067(19)63430-3

催化学报 ›› 2020, Vol. 41 ›› Issue (1): 72-81.DOI: 10.1016/S1872-2067(19)63430-3

Co(II)-空穴和Pt-电子助催化剂协同作用增强P掺杂g-C₃N₄光催化产氢性能

孙扣华^a,c, 沈珺^b, 刘芹芹^c,d, 唐华^c, 张明义^d, Syed Zulfiqar^c, 雷春生^a

a 常州大学环境与安全工程学院, 江苏常州 213164;
b 苏州卫生职业技术学院药学院, 江苏苏州 215009;
c 江苏大学材料科学与工程学院, 江苏镇江 212013;
d 哈尔滨师范大学光子与电子带隙材料教育部重点实验室, 黑龙江哈尔滨 150025

收稿日期:2019-05-30 修回日期:2019-06-22 出版日期:2020-01-18 发布日期:2019-10-22
通讯作者: 雷春生, 唐华
基金资助:
国家自然科学基金（51672113）；江苏省青蓝工程基金（201611）.

Synergistic effect of Co(II)-hole and Pt-electron cocatalysts for enhanced photocatalytic hydrogen evolution performance of P-doped g-C₃N₄

Kouhua Sun^a,c, Jun Shen^b, Qinqin Liu^c,d, Hua Tang^c, Mingyi Zhang^d, Syed Zulfiqar^c, Chunsheng Lei^a

a School of Environment & Safety Engineering, Changzhou University, Changzhou 213164, Jiangsu, China;
b School of Pharmacy, Suzhou Vocational Health College, Suzhou 215009, Jiangsu, China;
c School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu, China;
d Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, Harbin Normal University, Harbin 150025, Heilongjiang, China

Received:2019-05-30 Revised:2019-06-22 Online:2020-01-18 Published:2019-10-22
Supported by:
This work was supported by the National Natural Science Foundation of China (51672113) and QingLan Project Foundation of Jiangsu Province (201611).

摘要/Abstract

摘要： 石墨相氮化碳（g-C₃N₄）是一种新型的有机半导体材料，具有独特的层状结构、合适的能带位置、简单的制备方法以及出色的稳定性等特点，因而被广泛应用于光催化产氢领域.但是，较高的光生载流子的复合率和受限的迁移率大大地限制了g-C₃N₄的光催化产氢性能.目前，大量的研究证实块状g-C₃N₄的液相剥离、表面改性、元素掺杂、与其他半导体复合构筑异质结以及负载助催化剂等方法可以在一定程度上提高g-C₃N₄的光催化产氢性能.但是单一的g-C₃N₄改性方法往往并不能获得最理想的光催化产氢性能，因此，本文采用低温磷化法制备了二价钴（Co（Ⅱ））修饰的磷（P）掺杂的g-C₃N₄纳米片（Co（Ⅱ）/PCN），同时实现了掺杂P原子和负载空穴助催化剂Co（Ⅱ），该催化剂表现出出色的光催化产氢性能.在光催化制氢过程中，铂（Pt）纳米颗粒作为电子助催化剂成功的负载在Co（Ⅱ）/PCN上.光催化实验结果表明，最佳的Pt/Co（Ⅱ）/PCN复合材料光催化产氢速率达到774μmol·g^-1·h^-1，比纯相的g-C₃N₄纳米片（89.2μmol·g^-1·h^-1）提升8.6倍.同时优化的光催化剂具有良好的光催化稳定性，并在402nm处具有2.76%的量子产率.XRD，TEM，STEM-EDX和AFM结果证明，成功制备了纳米片状形貌的g-C₃N₄及其复合材料，催化剂中均匀的分布着Co和P元素.通过XPS证明了P-N的存在以及Co（Ⅱ）的存在，并且Co（Ⅱ）是以一种无定型的CoOOH的形式吸附在g-C₃N₄表面.光照后的TEM证明Pt颗粒成功的负载在Co（Ⅱ）/PCN表面.UV-visDRS表明，由于P的掺杂以及Co（Ⅱ）的修饰，Co（Ⅱ）/PCN相比于g-C₃N₄纳米片在可见光区域光吸收有了明显的增强.通过稳态和瞬态光致发光光谱分析，同时结合电化学分析表征（i-t、EIS）以及电子顺磁共振技术分析，证实了Co（Ⅱ）/PCN高效光催化性能的原因可能是由于更高效的光生载流子分离效率.本文对Pt/Co（Ⅱ）/PCN可能的光催化增强机理提出了设想.P的掺杂可以优化g-C₃N₄的电子结构，提高其光生载流子分离效率.而以Pt作为电子助催化剂，可以有效地捕获P掺杂的g-C₃N₄导带中的光生电子，进而发生水还原产氢反应；以Co（Ⅱ）作为空穴助催化剂，可以捕获价带中的光生空穴，进而发生三乙醇胺氧化反应.通过采用不同功能的助催化剂，实现P掺杂g-C₃N₄光生电子空穴的定向分流，促进了P掺杂g-C₃N₄的光生载流子的分离，从而提高催化剂的光催化产氢性能.本文可以为设计具有空穴-电子双助催化剂的光催化产氢系统提供一个新的思路.

关键词: 光催化产氢, 空穴助催化剂, 电子助催化剂, 磷掺杂氮化碳

Abstract: g-C₃N₄ is a metal-free semiconductor and a potential candidate for photocatalytic H₂ production, however, the drawbacks, rapid recombination rate and limited migration efficiency of photogenerated carriers, restrict its photocatalytic activity. Herein, Co(Ⅱ) as a hole cocatalyst modified P-doped g-C₃N₄ were successfully prepared to ameliorate the separation efficiency of photoinduced carriers and enhance the photocatalytic hydrogen production. The photocatalytic results demonstrated that the P-doped g-C₃N₄ (PCN) exhibited higher photocatalytic activity compared with pure g-C₃N₄, while Co(Ⅱ)/PCN photocatalyst exhibited further enhancement of photocatalytic performance. The proposed possible mechanism based on various characterizations is that P-doping can modulate the electronic structure of g-C₃N₄ to boost the separation of photogenerated-e^- and h⁺; while the synergistic effect of both Co(Ⅱ) (as hole cocatalyst) and Pt (as electron cocatalyst) can not only lead to the directional shunting of photogenerated e⁺-h^- pairs, but further accelerate the photogenerated electrons transfer to Pt in order to join the photocatalytic reduction process for hydrogen evolution. As a result, the transportation and separation of photoinduced carriers were accelerated to greatest extent in the Pt/Co(Ⅱ)/PCN photocatalyst.

Key words: Photocatalytic H₂ production, Hole cocatalyst, Electron cocatalyst, P-doped g-C₃N₄

孙扣华, 沈珺, 刘芹芹, 唐华, 张明义, Syed Zulfiqar, 雷春生. Co(II)-空穴和Pt-电子助催化剂协同作用增强P掺杂g-C₃N₄光催化产氢性能[J]. 催化学报, 2020, 41(1): 72-81.

Kouhua Sun, Jun Shen, Qinqin Liu, Hua Tang, Mingyi Zhang, Syed Zulfiqar, Chunsheng Lei. Synergistic effect of Co(II)-hole and Pt-electron cocatalysts for enhanced photocatalytic hydrogen evolution performance of P-doped g-C₃N₄[J]. Chinese Journal of Catalysis, 2020, 41(1): 72-81.

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Co(II)-空穴和Pt-电子助催化剂协同作用增强P掺杂g-C₃N₄光催化产氢性能

Synergistic effect of Co(II)-hole and Pt-electron cocatalysts for enhanced photocatalytic hydrogen evolution performance of P-doped g-C₃N₄

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