基于TiO2的光催化剂利用太阳能裂解水制氢研究进展

doi:10.16085/j.issn.1000-6613.2024-0376

化工进展 ›› 2025, Vol. 44 ›› Issue (3): 1298-1308.DOI: 10.16085/j.issn.1000-6613.2024-0376

基于TiO₂的光催化剂利用太阳能裂解水制氢研究进展

张馨儿¹^,²(), 裴刘军¹^,², 周雨蝶¹^,², 靳凯丽², 王际平¹^,²()

^1.上海工程技术大学纺织服装学院，上海 201620
^2.上海工程技术大学纺织化学清洁生产工程技术研究中心，上海 201620

收稿日期:2024-03-07 修回日期:2024-04-09 出版日期:2025-03-25 发布日期:2025-04-16
通讯作者: 王际平
作者简介:张馨儿（2000—），女，硕士研究生，研究方向为TiO₂催化剂、油水分离。E-mail：1476825117@qq.com。
基金资助:
国家自然科学基金(22072089);安徽省重点研发项目(2023t07020001);海宁市科技计划工业、农业项目(2021003);松江区科学技术攻关项目(23SJJBGS2);浙江省清洁染整技术研究重点实验室开放基金(QJRZ2301)

Progress of TiO₂-based photocatalysts for hydrogen production by water splitting with solar energy

ZHANG Xin’er¹^,²(), PEI Liujun¹^,², ZHOU Yudie¹^,², JIN Kaili², WANG Jiping¹^,²()

^1.School of Textiles and Fashion Engineering, Shanghai University of Engineering Science, Shanghai 201620, China
^2.Engineering Research Center of Textile Chemistry and Clean Production, Shanghai University of Engineering Science, Shanghai 201620, China

Received:2024-03-07 Revised:2024-04-09 Online:2025-03-25 Published:2025-04-16
Contact: WANG Jiping

摘要/Abstract

摘要：

太阳能裂解水制氢是储存太阳能的有效方法，可将光子转化为化学能。TiO₂是太阳能驱动氢演化的最佳材料之一，但电子空穴对分离不良会限制其活性，而TiO₂光催化剂与助催化剂结合可提高析氢性能。因此，本文详细回顾了金属类助催化剂对TiO₂光催化制氢效果提升的相关研究，着重介绍了贵金属基助催化剂、非贵金属基助催化剂、金属硫化物和金属磷化物助催化剂、双金属基助催化剂。这些研究揭示了各种助催化剂对提升TiO₂光催化效率的关键作用，展示了太阳能裂解水产氢技术的广阔应用前景。此外，为了更全面地理解这项技术，本文还深入介绍了半导体光催化制氢的详细演化机理：包括反应物的吸附、光激发过程、电子和空穴的迁移以及还原/氧化反应。通过深入剖析这些反应步骤，有望为科研人员提供一个清晰的理论框架，以便更好地制备和优化TiO₂光催化中的助催化剂，同时深刻理解氢气演化的内在机制。最后对TiO₂基光催化剂进行了总结与展望：即对不同种类的助催化剂的优劣势对比分析，并为光诱导析氢催化剂中的TiO₂负载活性位点的定制提供丰富的思路。

关键词: 二氧化钛基, 光催化剂, 制氢, 太阳能裂解水

Abstract:

Solar water splitting for hydrogen production is an effective method for storing solar energy and converting photons into chemical energy. TiO₂ is one of the best materials for solar-driven hydrogen evolution, but poor separation of electron-hole pairs limits its activity, and the combination of TiO₂ photocatalysts and co-catalysts improves hydrogen precipitation performance. Therefore, this paper reviewed in detail the studies related to the enhancement of TiO₂ photocatalytic hydrogen production by metal-based co-catalysts, focusing on noble metal-based co-catalysts, non-precious metal-based co-catalysts, metal-sulfide and metal-phosphide co-catalysts, and bimetallic-based co-catalysts. These studies revealed the key roles of various co-catalysts in enhancing the photocatalytic efficiency of TiO₂, demonstrating the broad application prospects of solar cracking hydrogeneration technology. In addition, for a more comprehensive understanding of this technology, this paper provided an in-depth description of the detailed evolutionary mechanism of semiconductor photocatalytic hydrogen production: including reactant adsorption, photoexcitation process, electron and hole migration, and reduction/oxidation reactions. The in-depth analysis of these reaction steps was expected to provide researchers with a clear theoretical framework for better preparation and optimization of co-catalysts in TiO₂ photocatalysis, as well as a deep understanding of the intrinsic mechanism of hydrogen evolution. Finally, the TiO₂-based photocatalysts were summarized and prospected: i.e., the advantages and disadvantages of different kinds of co-catalysts were compared and analyzed, and abundant ideas were provided for the customization of TiO₂-loaded active sites in photo-induced hydrogen precipitation catalysts.

Key words: TiO₂-based, photocatalysts, hydrogen production, solar water splitting

中图分类号:

TB31

张馨儿, 裴刘军, 周雨蝶, 靳凯丽, 王际平. 基于TiO₂的光催化剂利用太阳能裂解水制氢研究进展[J]. 化工进展, 2025, 44(3): 1298-1308.

ZHANG Xin’er, PEI Liujun, ZHOU Yudie, JIN Kaili, WANG Jiping. Progress of TiO₂-based photocatalysts for hydrogen production by water splitting with solar energy[J]. Chemical Industry and Engineering Progress, 2025, 44(3): 1298-1308.

图/表 7

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催化剂	助催化剂修饰方法	测试条件	产氢率	参考文献
TiO₂/RuO₂/CuO	一步溶胶-凝胶工艺	450W高压汞灯照射	20.7mmol/(h·g)	[54]
Pt@TiO₂	原位水热反应	300W Xe灯为光源的斩波光照射	4.389mmol/(h·g)	[55]
Au/WO₃/TiO₂	溶胶-凝胶辅助光沉积法	紫外可见光照射	17.2mmol/(h·g)	[56]
CdTe/Ag/TiO₂	水热法	紫外可见光照射	53.0μmol/(h·cm²)	[57]
Ni/C/TiO₂	水解-煅烧法	300W Xe灯为光源的斩波光照射	1745.0μmol/(h·g)	[58]
CaTiO₃/Cu/TiO₂	两步水热法	模拟太阳光照射	0.253mmol/(h·g)	[59]
TiO₂/MoC@C	超声辅助沉积法	紫外可见光照射	504μmol/(h·g)	[60]
Ti₃CN@TiO₂/CdS	原位生长法	420nm滤光片的300W氙灯照射	3393.4μmol/(h·g)	[61]
CdS/TiO₂	水热法	紫外可见光照射	5791mL/(h·g)	[62]
Au-BaO@TiO₂/CdS	水热法	100W氙灯为光源照射	13.54μmol/(h·g)	[63]
Co₂P/P-TiO₂/2H-1T MoS₂	水热法和磷化法	紫外可见光照射	4156μmol/(h·g)	[64]
TiO₂@CuS	水热法	全光谱/近红外光照射	2467/173μmol/(h·g)	[65]
CoP/Co₂P@TiO₂	低温磷化法	模拟太阳光的照射	824.5μmol/(h·g)	[66]
Ni₂P/TiO₂	溶胶-凝胶法	紫外可见光照射	1300μmol/(h·g)	[67]
Ni-P@CeO₂-TiO₂	热分解和沉积/还原法	太阳光和太阳模拟器的照射	1300μmol/(h·g)	[68]
MoS _x -rGO/TiO₂	两步光催化还原法	紫外可见光照射	150.1μmol/(h·g)	[69]
1PtAu-TiO₂	两步沉积-沉淀法	模拟太阳光照射	61.3μmol/(h·g)	[70]
TiO₂@RuO₂	一步静电纺丝和高温煅烧法	300W氙灯作为全光谱范围内的光源	1489.3μmol/(h·g)	[71]

催化剂	助催化剂修饰方法	测试条件	产氢率	参考文献
TiO₂/RuO₂/CuO	一步溶胶-凝胶工艺	450W高压汞灯照射	20.7mmol/(h·g)	[54]
Pt@TiO₂	原位水热反应	300W Xe灯为光源的斩波光照射	4.389mmol/(h·g)	[55]
Au/WO₃/TiO₂	溶胶-凝胶辅助光沉积法	紫外可见光照射	17.2mmol/(h·g)	[56]
CdTe/Ag/TiO₂	水热法	紫外可见光照射	53.0μmol/(h·cm²)	[57]
Ni/C/TiO₂	水解-煅烧法	300W Xe灯为光源的斩波光照射	1745.0μmol/(h·g)	[58]
CaTiO₃/Cu/TiO₂	两步水热法	模拟太阳光照射	0.253mmol/(h·g)	[59]
TiO₂/MoC@C	超声辅助沉积法	紫外可见光照射	504μmol/(h·g)	[60]
Ti₃CN@TiO₂/CdS	原位生长法	420nm滤光片的300W氙灯照射	3393.4μmol/(h·g)	[61]
CdS/TiO₂	水热法	紫外可见光照射	5791mL/(h·g)	[62]
Au-BaO@TiO₂/CdS	水热法	100W氙灯为光源照射	13.54μmol/(h·g)	[63]
Co₂P/P-TiO₂/2H-1T MoS₂	水热法和磷化法	紫外可见光照射	4156μmol/(h·g)	[64]
TiO₂@CuS	水热法	全光谱/近红外光照射	2467/173μmol/(h·g)	[65]
CoP/Co₂P@TiO₂	低温磷化法	模拟太阳光的照射	824.5μmol/(h·g)	[66]
Ni₂P/TiO₂	溶胶-凝胶法	紫外可见光照射	1300μmol/(h·g)	[67]
Ni-P@CeO₂-TiO₂	热分解和沉积/还原法	太阳光和太阳模拟器的照射	1300μmol/(h·g)	[68]
MoS _x -rGO/TiO₂	两步光催化还原法	紫外可见光照射	150.1μmol/(h·g)	[69]
1PtAu-TiO₂	两步沉积-沉淀法	模拟太阳光照射	61.3μmol/(h·g)	[70]
TiO₂@RuO₂	一步静电纺丝和高温煅烧法	300W氙灯作为全光谱范围内的光源	1489.3μmol/(h·g)	[71]

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基于TiO₂的光催化剂利用太阳能裂解水制氢研究进展

Progress of TiO₂-based photocatalysts for hydrogen production by water splitting with solar energy

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