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

doi:10.11949/0438-1157.20230323

Abstract

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

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

CLC Number:

TQ 134.1

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.

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.

Figures/Tables 10

References 42

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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]

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]

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

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

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

Ni@C@TiO₂核壳双重异质结的构筑及光热催化分解水产氢

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