Ni@C@TiO2核壳双重异质结的构筑及光热催化分解水产氢

doi:10.11949/0438-1157.20230323

化工学报 ›› 2023, Vol. 74 ›› Issue (6): 2458-2467.DOI: 10.11949/0438-1157.20230323

• 催化、动力学与反应器 • 上一篇下一篇

Ni@C@TiO₂核壳双重异质结的构筑及光热催化分解水产氢

李勇¹(), 高佳琦¹, 杜超¹, 赵亚丽¹(), 李伯琼¹, 申倩倩², 贾虎生², 薛晋波²()

^1.晋中学院材料科学与工程系，轻质材料改性应用山西省协同创新中心，山西晋中 030619
^2.太原理工大学新材料界面科学与工程教育部重点实验室，山西太原 030024

收稿日期:2023-04-04 修回日期:2023-06-10 出版日期:2023-06-05 发布日期:2023-07-27
通讯作者: 赵亚丽,薛晋波
作者简介:李勇（1987—），男，博士，讲师，lytyut@126.com
基金资助:
国家自然科学基金项目(62105131);山西省自然科学基金项目(202203021212508);山西省科技创新青年人才团队项目(202204051001005);晋中市科技重点研发项目(Y201027);山西省高等学校科技创新项目(2022L491)

Construction of Ni@C@TiO₂ core-shell dual-heterojunctions for advanced photo-thermal catalytic hydrogen generation

Yong LI¹(), Jiaqi GAO¹, Chao DU¹, Yali ZHAO¹(), Boqiong LI¹, Qianqian SHEN², Husheng JIA², Jinbo XUE²()

^1.Department of Materials Science and Engineering, Shanxi Province Collaborative Innovation Center for Light Materials Modification and Application, Jinzhong University, Jinzhong 030619, Shanxi, China
^2.Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024, Shanxi, China

Received:2023-04-04 Revised:2023-06-10 Online:2023-06-05 Published:2023-07-27
Contact: Yali ZHAO, Jinbo XUE

摘要/Abstract

摘要：

合理设计具有出色光吸收和电荷分离与转移能力的纳米催化剂，实现高效的光催化制氢仍然是一个挑战。借助间苯二酚-甲醛树脂（RF）模板和Ar气氛煅烧工艺构建了三元Ni@C@TiO₂核壳双重异质结纳米催化剂，实现了高效热积聚和高通量电荷转移。该体系充分结合了碳层的宽带吸收、Ni纳米粒子（NPs）的等离激元特性以及TiO₂的保护和催化功能。在双重异质结中建立了较大的内部电场，使电荷分离效率提高了2.4倍。得益于Ni@C芯光热效应与Ni/C-C/TiO₂双重异质结的协同效应，从而实现有效的电荷分离和传输，提高了电荷转移速率；核壳结构的构建降低了体系热量损耗，最终实现高效的太阳能光热转换（光热效率78.0%）和光热催化分解水产氢性能（析氢速率为1538 μmol·g^-1·h^-1）的提升。稳健的核壳纳米颗粒可以应用到其他光热催化系统的设计中，为开发更高效的全光谱利用型光催化剂提供思路。

关键词: 催化剂, 制氢, 纳米粒子, 异质结, 等离激元, 核壳结构

Abstract:

Photo-thermal synergistic catalysis coupling photo-chemical and thermo-chemical conversions integrates the benefits of both high driving force of photocatalysis and high selectivity of thermocatalysis. It is one of the most promising methods to enhance its catalytic efficiency. Unfortunately, rapid heat loss and fast charge carrier recombination seriously affect its solar energy utilization and conversion efficiency. Herein, a hierarchical Ni@C@TiO₂ core-shell dual-heterojunctions is prepared by resorcinol formaldehyde (RF) template and Ar calcination process to realize efficient heat accumulation and high-flux charge transfer for achieving advanced photo-thermal catalytic hydrogen performance. This system fully combines the broadband absorption of carbon layer and plasmonic property of Ni core. A giant internal electric field (IEF) in the dual-heterojunctions is built, enabling the charge transfer efficiency to be enhanced by 2.4 times. Benefiting from the synergistic effect between Ni@C core photo-thermal effect and Ni/C and C/TiO₂ dual-heterojunctions, an excellent photo-thermal efficiency of 78.0% and the performance of photo-thermal catalytic water splitting for hydrogen production hydrogen evolution rate is (1538 μmol·g^-1·h^-1) are eventually improved. Robust core-shell nanoparticles can be applied to the design of other photo-thermal catalytic systems, providing ideas for the development of more efficient full-spectrum utilization photocatalysts.

Key words: catalyst, hydrogen production, nanoparticles, heterojunction, plasmonic, core-shell

中图分类号:

TQ 134.1

李勇, 高佳琦, 杜超, 赵亚丽, 李伯琼, 申倩倩, 贾虎生, 薛晋波. Ni@C@TiO₂核壳双重异质结的构筑及光热催化分解水产氢[J]. 化工学报, 2023, 74(6): 2458-2467.

Yong LI, Jiaqi GAO, Chao DU, Yali ZHAO, Boqiong LI, Qianqian SHEN, Husheng JIA, Jinbo XUE. Construction of Ni@C@TiO₂ core-shell dual-heterojunctions for advanced photo-thermal catalytic hydrogen generation[J]. CIESC Journal, 2023, 74(6): 2458-2467.

图/表 10

图1 Ni@C@TiO2双重异质结的合成示意图

Fig.1 Schematic diagram of the synthesis of hierarchical Ni@C@TiO2 dual-heterojunctions

图2 Ni@RF、Ni@RF@TiO2、Ni@C和Ni@C@TiO2的XRD谱图

Fig.2 XRD patterns of Ni@RF, Ni@RF@TiO2, Ni@C and Ni@C@TiO2

图3 Ni NPs、 Ni@RF和Ni@C@TiO2的SEM图；Ni@RF@TiO2和Ni@C@TiO2的TEM图；Ni@C@TiO2的STEM图及对应的EDX图

Fig.3 SEM images of Ni NPs, Ni@RF and Ni@C@TiO2； TEM images of Ni@RF@TiO2 and Ni@C@TiO2；STEM images and EDX elemental mappings of Ni@C@TiO2

图4 在模拟太阳光AM 1.5G（100 mW·cm-2）照射下样品的光催化和光热催化产氢性能

Fig.4 Photocatalytic and photo-thermal catalytic hydrogen production performances of samples under AM 1.5G simulated sunlight (100 mW·cm-2)

表1 不同NPs样品在不同反应条件下的催化活性

Table 1 Catalytic activities in different reaction conditions over different samples

催化剂

PC/

(μmol·g^-1·h^-1)

PTC/

(μmol·g^-1·h^-1)

C@TiO₂

Ni@TiO₂

表2 C/TiO2基催化剂的光解水产氢性能对比

Table 2 Hydrogen evolution of C/TiO2 based photocatalysts

催化剂	助催化剂	牺牲剂	光源	产氢活性/（μmol·g^-1·h^-1）	文献
Ni@C@TiO₂	—	三乙醇胺	300 W氙灯，AM 1.5G	1538	本工作
C@TiO₂/TiO_2-_x	—	三乙醇胺	300 W氙灯，AM 1.5G	3667	[20]
BFBA‐TiO₂	—	三乙醇胺	300 W氙灯	228.2 (λ>420 nm)	[27]
B-TiO₂/g-C₃N₄	—	三乙醇胺	300 W氙灯	808.97	[28]
C@TiO_2-_x /CNNS	3%（质量） Pt	三乙醇胺	300 W氙灯	1830.93	[29]
Cu-TiO₂@C	—	甲醇	300 W氙灯	269.1	[30]
Cr₂O₃/C@TiO₂	—	甲醇	300 W氙灯	446	[31]
VTi@CQDs@rGO	—	甲醇	—	638	[32]
Li-EDA处理P-25	—	甲醇	模拟全光谱	3460	[33]
b-C-N-S-TiO₂	—	甲醇	300 W氙灯，AM 1.5G	149.7	[34]
Pt负载金红石H-TiO₂	0.57%（质量） Pt	甲醇	300 W氙灯	3320	[35]

图5 在模拟太阳光AM 1.5G（100 mW·cm-2）照射下样品的光热转换性能

Fig.5 Photo-thermal conversion performances of samples under AM 1.5G simulated sunlight (100 mW·cm-2)

表3 样品的光热特性

Table 3 Photo-thermal properties of the as-prepared samples

样品	ΔT_max/℃	时间常数τ_s/s	光热转换效率η/%
Ni@TiO₂	19.1	266.42	58.1
C@TiO₂	15.3	332.92	36.6
Ni@C@TiO₂	24.5	257.70	78.0

图6 在模拟太阳光AM 1.5G（100 mW·cm-2）照射下样品的载流子动力学

Fig.6 The carrier dynamics of as-prepared samples under AM 1.5G simulated sunlight (100 mW·cm-2)

图7 Ni@C@TiO2光热和光化学协同作用产氢的机理

Fig.7 Mechanism of the synergetic photo-thermal and photo-chemical effect on H2 generation over Ni@C@TiO2

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Ni@C@TiO₂核壳双重异质结的构筑及光热催化分解水产氢

Construction of Ni@C@TiO₂ core-shell dual-heterojunctions for advanced photo-thermal catalytic hydrogen generation

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