硫基光催化剂在高效光催化制氢中研究进展

doi:10.11949/0438-1157.20251084

摘要/Abstract

摘要：

工业化的快速推进加剧了全球对能源消耗与碳排放的担忧，氢能以其燃烧产物仅为水、来源丰富且燃烧热值高成为绿色能源体系的关键组成部分。光催化分解水制氢作为一种极具潜力的氢能生产技术，其效率和实用性受可见光利用率低、光生电荷载流子快速复合等因素制约。硫基光催化剂凭借硫掺杂带来的优势，在光催化领域展现出显著潜力，可通过修饰材料能带结构拓宽光响应范围、增强稳定性并抑制电荷复合。综述了硫基催化剂在光催化制氢中的最新研究进展，重点探讨了CdS、In₂S₃、ZnS、ZnIn₂S₄和CdZnS等典型硫基光催化剂的特性及改性策略，通过形貌工程、元素掺杂和负载助催化剂等手段，可有效提升光催化剂性能。本文为开发高效、稳定的光催化制氢催化剂提供了理论基础，助力全球能源结构向绿色转型。

关键词: 光催化制氢, 硫基光催化剂, 催化剂优化, 异质结, 助催化剂

Abstract:

The accelerated industrialization has intensified global concerns over energy consumption and carbon emissions. Hydrogen energy, characterized by water-only combustion products, abundant availability, and high calorific value, constitutes a pivotal element in future energy systems. Photocatalytic water splitting represents a promising strategy for clean hydrogen production; however, its efficiency and practicality are limited by the constrained utilization of visible light and rapid recombination of photogenerated charges. Sulfide-based catalysts leverage the advantages of sulfur doping to modify band structures, broadening the light response range, enhancing stability, and suppressing charge recombination. This review synthesizes recent advances in sulfide-based photocatalysts for hydrogen evolution, focusing on characteristic properties and modification approaches for representative systems including CdS, In₂S₃, ZnS, ZnIn₂S₄, and CdZnS. Performance enhancements are achieved through morphology engineering, elemental doping, and cocatalyst integration. Through the design of sulfur vacancies, the cyclic regeneration of sulfide-based materials is achieved, reducing reliance on precious metals, which aligns with the sustainability requirements for renewable materials. Collectively, this work establishes fundamental principles for developing efficient, stable photocatalytic systems, paving the way toward sustainable energy infrastructure transformation.

Key words: photocatalytic hydrogen production, sulfur-based photocatalyst, catalyst optimization, heterojunctions, co-catalyst

中图分类号:

TQ426.94

张晨阳, 顾春鹏, 韩长存. 硫基光催化剂在高效光催化制氢中研究进展[J]. 化工学报, DOI: 10.11949/0438-1157.20251084.

Chenyang ZHANG, Chunpeng GU, Changcun HAN. Recent advances and perspectives on sulfide-based photocatalysts for hydrogen production[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251084.

图/表 21

图1 光催化反应的基本步骤

Fig.1 The basic steps involved in a photocatalytic reaction

图2 （a）电荷分离及光催化机理示意图；（b）PANI和NCPP的CdS纳米棒示意图[30]

Fig.2 (a) Diagram illustrating charge separation and photocatalytic mechanism;(b) schematic of CdS nanorods loaded with PANI and NCPP[30]

图3 （a）Ni@NiSx-CdS光催化剂的合成过程示意图；（b）不同CdS基光催化剂的析氢速率对比图[29]

Fig.3 (a) Schematic of the synthetic process; (b) comparison of the H2 evolution rate with other photocatalysts in recent works[29]

图4 PdS/In2S3催化剂的（a）制备流程示意图和（b）内建电场形成示意图；负载不同助催化剂和不同负载量的（c）产氢速率对比图和（d）产氢性能图；（e）3PdS/In2S3产氢稳定性测试[35]

Fig.4 Schematic illustration of (a)the fabrication for PdS/In2S3 catalyst and(b)the internal electric field formation between PdS and In2S3, Comparison of the hydrogen evolution rate (c) and amount of H2 generation(d)for the as-prepared samples;(e)stability test of H2 generation for the 3PdS/In2S3 composite[35]

图5 透射电镜（TEM）图像：（a）CoSx；（b）CoSx@In2S3和（c）CoSx@Vs-In2S3；（d）光催化产氢性能图；CoSx@Vs-In2S3核壳光催化剂的（e）稳定性测试、（f）循环产氢测试和（g）产氢反应机制示意图[36]

Fig.5 (a–c) Transmission Electron Microscope(TEM) images of CoSx, CoSx@In2S3, and CoSx@Vs – In2S3, (d) Photocatalytic hydrogen-evolution rate of CoSx,In2S3, CoSx@In2S3, and CoSx@Vs – In2S3 catalysts; (e) uninterrupted stability tests of the CoSx@Vs – In2S3 core/shell photocatalysts;(f) recycling hydrogen-generation tests of the CoSx@Vs – In2S3 core/shell photocatalysts; (g)reaction mechanism for photocatalytic hydrogen evolution on the S-scheme CoSx@Vs – In2S3 heterojunction[36]

图6 （a）P-In2S3样品的制备流程示意图；（b）AQY；（c）基于光吸收光谱的带隙计算；P-In2S3样品的（d）扫描电子显微镜（SEM）、（e）TEM、（f）HRTEM图像，后方的四个方框区域显示了傅里叶变换；（g）不同样品的累积产氢量；（h）P-In2S3的七次光催化产氢循环与纯In2S3的四次循环对比[37]

Fig.6 (a)The schematic of the fabrication process of the sample P-In2S3,(b)the light absorption spectra and AQY, (c) the bandgap calculation based on the light absorption spectra,(d)the SEM image, (e) the TEM image, (f) the High-resolution SEM(HRTEM) image of the P-In2S3 sample. The Fourier transforms of the image involving the four box areas are displayed,(g) accumulated amount of hydrogen production of different samples, (h) seven photocatalytic hydrogen production cycles of the P-In2S3 vs. four cycles of the bare In2S3[37]

图7 ZnO/ZnS异质结构纳米棒阵列的（a）高分辨率SEM图像、（b）HRTEM图像；（c）ZnO核（黑色）上ZnS（灰色）壳的阴离子交换生长反应方案；（d）电荷转移过程[39]

Fig.7 (a)HRTEM images of ZnO/ZnS HNAs; inset: the crystallographic character of the single crystal ZnO core and the polycrystalline ZnS shell; (b) HRTEM images of a single ZnO/ZnS HNR; (c) scheme of the anion-exchange growing reaction for ZnS (grey) shell on ZnO core (black); (d) the charge-transfer process in ZnO/ZnS HNRAs[39]

图8 （a）ZCZ-3的循环稳定性测试和（b）光催化析氢反应前后的XRD谱图[40]

Fig.8 (a)Cycle stability test of the ZCZ-3 and (b) XRD before and after photocatalytic hydrogen evolution reaction[40]

图9 M-ZIS的（a）SEM和（b）AC-TEM图；H-ZIS的（c）SEM和（d）AC-TEM[45]

Fig.9 (a)SEM and (b)AC-TEM of M-ZIS; (c)SEM and (d)AC-TEM of H-ZIS[45]

图10 （a）B-ZIS和（b）M-ZIS的TEM图像；B-ZIS、M-ZIS和M-ZIS-s的（c）拉曼光谱和（d）UV-vis 吸收光谱图[46]

Fig.10 The TEM images of (a)B-ZIS and (b)M-ZIS; (c) The Raman spectra and (d)UV–vis DRS of B-ZIS, M-ZIS and M-ZIS-S[46]

图11 （a）Ni/ZnIn2S4的合成过程示意图；（b）2 wt% Ni/ZnIn2S4的SEM图像；（c）ZnIn2S4和2 wt% Ni/ZnIn2S4的析氢反应机理示意图[47]

Fig.11 (a)the schematic synthetic process of Ni/ZnIn2S4;(b) SEM images of 2 wt%-Ni/ZnIn2S4;(c) the schemed mechanism of ZnIn2S4 and 2 wt%-Ni/ZnIn2S4 for H2 evolution[47]

图12 TEM图像：（a–c）ZnS(en)0.5、（d–f）Cd0.5Zn0.5S（en）x和（g–i）Cd0.5Zn0.5S纳米片[51]

Fig.12 TEM images of ZnS(en)0.5 (a–c), Cd0.5Zn0.5S(en)x (d–f), and Cd0.5Zn0.5S (g–i) nanosheets[51]

图13 CZS纳米棒的（a）SEM、（b）TEM和（c，d）HRTEM图像；（e）CdS、ZnS、CZS和1.0 wt% Pt/CZS的光催化析氢速率；（f）CZS在可见光照射下25 h的光催化稳定性[52]

Fig.13 (a) SEM, (b) TEM, and (c, d) HRTEM images of CZS nanorods; (e) Photocatalytic hydrogen evolution rates of CdS, ZnS, CZS, and 1.0 wt% Pt/CZS; (f) Photocatalytic stability of CZS under visible light irradiation for 25 h[52]

图14 （a-c）15 wt% NiB/ZnCdS的TEM图像；x wt% NiB/ZnCdS样品的（d）析氢量、（e）析氢速率、（f）AQY和（g）UV-vis吸收光谱；（h）15 wt% NiB/ZnCdS经5次循环后的析氢量和（i）稳定性[53]

Fig.14 (a-c)TEM image of 15 wt% NiB/ZnCdS(d) The H2 production amount of x wt% NiB/ZnCdS samples; (e)the H2 production rate of ZnCdS and NiB/ZnCdS;(f) the apparent quantum yields of ZnCdS samples with different contents of NiB;(g)UV-vis absorption spectra of NiB/ZnCdS samples and pure ZnCdS;(h)the H2 production amount of 15 wt% NiB/ZnCdS after 5 cycles;(i)the stability of 15 wt% NiB/ZnCdS[53]

表1 典型硫基光催化剂析氢性能汇总表

Table 1 Summary Table of Hydrogen Evolution Performance of Typical Sulfide-Based Photocatalysts

催化剂基体类型	具体催化剂体系	析氢速率/ mmol·g^-1·h^-1	相对于纯相的提升倍数	突出特点	光源	空穴牺牲剂	AQY	文献
CdS	PANI/NCPP/CdS	170.3	426	双功能助催化剂（NiCoP/NiCoPi）+导电聚合物，质子吸附强化	可见光（λ>420 nm）	乳酸	49%（420 nm）	[30]
	Ni@NiS_x-CdS	78.7	18.3	非晶-晶态异质结+ Cd-S-Ni键桥，梯度功函数驱动电子迁移	可见光	乳酸		[29]
	中空CdS（{101}晶面）			模板辅助阳离子交换制备，中空结构增强光吸收、缩短载流子迁移距离	可见光			[31]
	NiCoP-g-C₃N₄/CdS	55.63	4.6	异质结构建+双助催化协同，量化电荷分离效率差异	可见光	乳酸	70%（420 nm）	[32]
In₂S₃	PdS/In₂S₃（3 wt% PdS）	142.27	149.8	0D-2D异质结+Pd-S-In键，内建电场定向转移空穴	可见光	0.35 M Na₂S+0.25 M Na₂SO₃		[35]
	CoS_x@V_s-In₂S₃	4.136	8.23	核-壳异质结+硫空位，In原子为高效析氢中心	可见光	0.35 M Na₂S+0.25 M Na₂SO₃		[36]
	P-In₂S₃（等离子体风表面非晶化）	4.57	2.7	晶-非晶界面，S原子富集电子，抗光腐蚀	可见光	TEOA	26.2%（380 nm）	[37]
	In₂S₃-WO₃	5.1	5	2D-1D Type-II异质结，WO₃抑制光腐蚀、促进电荷分离	AM 1.5G 模拟太阳光	0.5 M Na₂SO₄		[38]
ZnS	ZnO/ZnS HNRAs	384	451.8	n-p异质结，电子空穴跨界面转移，延长载流子寿命	模拟太阳光	无牺牲剂		[39]
	ZnIn₂S₄/CNTs/ZnS（ZCZ-3）	未明确（活性稳定）		三元异质结，ZnS结构稳定，抗分解抗变质	未明确	未明确		[40]
	CdS/CuS/ZnS（C₂C₅）	6.401	4	Cd-Cu 共掺杂+三元异质结+硫/锌空位陷阱	AM 1.5G 模拟太阳光	0.35 M Na₂S+0.25 M Na₂SO₃	38.3%（425 nm）	[41]
ZnIn₂S₄	M-ZIS（有序晶格）	0.0082	2.5	微波辅助制备，晶格有序，载流子分离效率优	可见光	TEOA		[45]
	H-ZIS（硫空位缺陷）	0.0033		硫空位丰富、晶格无序，缺陷充当复合中心	可见光	TEOA		[45]
	M-ZIS-S（硫空位修饰）	未明确（光吸收提升）		硫空位窄化带隙，比表面积提升至 82.53 m²・g⁻¹	可见光	TEOA		[46]
	Ni/ZnIn₂S₄（2 wt% Ni簇）	22.2	10.6	Ni簇提供活性位点，加速电子-空穴分离与迁移	可见光	TEOA	56.14%（450 nm）	[47]
	ZnIn₂S₄/N-rGO	2.85	9.7	S型异质结+N掺杂rGO，增强电子传输与光吸收	可见光	TEOA	27.24%（420 nm）	[48]
CdZnS	纯相CdZnS	1.395		固溶体，可调控带隙，高比表面积	可见光	无（纯水）		[44]
	Cd_0.5Zn_0.5S(en)ₓ（二维介孔超薄）	1.395		模板转化法制备，厚度1.5 nm，孔径20.6 nm，高活性位点	可见光	无（纯水）		[51]
	Cd_0.6Zn_0.4S（1D纳米棒+硫空位）	59.3	20	堆叠缺陷+硫空位，电子捕获位点丰富，电荷传输路径短	可见光	0.35 M Na₂S+0.25 M Na₂SO₃		[52]
	NiB/CdZnS（15 wt% NiB）	8.137	17	非晶态NiB负载，不饱和配位原子为高效析氢中心	可见光	TEOA	13.3%（AQY）	[53]
	Mo-Zn₀.5Cd₀.5S@NiCo₂S₄	未明确（双功能活性）		掺杂-异质结协同，提升析氢与降解双功能	可见光			[49]
	CdZnS@Ti₃C₂Tx MXene	未明确（活性提升）		原位生长异质结，MXene增强电子传输	可见光	TEOA		[50]

表1 典型硫基光催化剂析氢性能汇总表

Table 1 Summary Table of Hydrogen Evolution Performance of Typical Sulfide-Based Photocatalysts

催化剂基体类型	具体催化剂体系	析氢速率/ mmol·g^-1·h^-1	相对于纯相的提升倍数	突出特点	光源	空穴牺牲剂	AQY	文献
CdS	PANI/NCPP/CdS	170.3	426	双功能助催化剂（NiCoP/NiCoPi）+导电聚合物，质子吸附强化	可见光（λ>420 nm）	乳酸	49%（420 nm）	[30]
	Ni@NiS_x-CdS	78.7	18.3	非晶-晶态异质结+ Cd-S-Ni键桥，梯度功函数驱动电子迁移	可见光	乳酸		[29]
	中空CdS（{101}晶面）			模板辅助阳离子交换制备，中空结构增强光吸收、缩短载流子迁移距离	可见光			[31]
	NiCoP-g-C₃N₄/CdS	55.63	4.6	异质结构建+双助催化协同，量化电荷分离效率差异	可见光	乳酸	70%（420 nm）	[32]
In₂S₃	PdS/In₂S₃（3 wt% PdS）	142.27	149.8	0D-2D异质结+Pd-S-In键，内建电场定向转移空穴	可见光	0.35 M Na₂S+0.25 M Na₂SO₃		[35]
	CoS_x@V_s-In₂S₃	4.136	8.23	核-壳异质结+硫空位，In原子为高效析氢中心	可见光	0.35 M Na₂S+0.25 M Na₂SO₃		[36]
	P-In₂S₃（等离子体风表面非晶化）	4.57	2.7	晶-非晶界面，S原子富集电子，抗光腐蚀	可见光	TEOA	26.2%（380 nm）	[37]
	In₂S₃-WO₃	5.1	5	2D-1D Type-II异质结，WO₃抑制光腐蚀、促进电荷分离	AM 1.5G 模拟太阳光	0.5 M Na₂SO₄		[38]
ZnS	ZnO/ZnS HNRAs	384	451.8	n-p异质结，电子空穴跨界面转移，延长载流子寿命	模拟太阳光	无牺牲剂		[39]
	ZnIn₂S₄/CNTs/ZnS（ZCZ-3）	未明确（活性稳定）		三元异质结，ZnS结构稳定，抗分解抗变质	未明确	未明确		[40]
	CdS/CuS/ZnS（C₂C₅）	6.401	4	Cd-Cu 共掺杂+三元异质结+硫/锌空位陷阱	AM 1.5G 模拟太阳光	0.35 M Na₂S+0.25 M Na₂SO₃	38.3%（425 nm）	[41]
ZnIn₂S₄	M-ZIS（有序晶格）	0.0082	2.5	微波辅助制备，晶格有序，载流子分离效率优	可见光	TEOA		[45]
	H-ZIS（硫空位缺陷）	0.0033		硫空位丰富、晶格无序，缺陷充当复合中心	可见光	TEOA		[45]
	M-ZIS-S（硫空位修饰）	未明确（光吸收提升）		硫空位窄化带隙，比表面积提升至 82.53 m²・g⁻¹	可见光	TEOA		[46]
	Ni/ZnIn₂S₄（2 wt% Ni簇）	22.2	10.6	Ni簇提供活性位点，加速电子-空穴分离与迁移	可见光	TEOA	56.14%（450 nm）	[47]
	ZnIn₂S₄/N-rGO	2.85	9.7	S型异质结+N掺杂rGO，增强电子传输与光吸收	可见光	TEOA	27.24%（420 nm）	[48]
CdZnS	纯相CdZnS	1.395		固溶体，可调控带隙，高比表面积	可见光	无（纯水）		[44]
	Cd_0.5Zn_0.5S(en)ₓ（二维介孔超薄）	1.395		模板转化法制备，厚度1.5 nm，孔径20.6 nm，高活性位点	可见光	无（纯水）		[51]
	Cd_0.6Zn_0.4S（1D纳米棒+硫空位）	59.3	20	堆叠缺陷+硫空位，电子捕获位点丰富，电荷传输路径短	可见光	0.35 M Na₂S+0.25 M Na₂SO₃		[52]
	NiB/CdZnS（15 wt% NiB）	8.137	17	非晶态NiB负载，不饱和配位原子为高效析氢中心	可见光	TEOA	13.3%（AQY）	[53]
	Mo-Zn₀.5Cd₀.5S@NiCo₂S₄	未明确（双功能活性）		掺杂-异质结协同，提升析氢与降解双功能	可见光			[49]
	CdZnS@Ti₃C₂Tx MXene	未明确（活性提升）		原位生长异质结，MXene增强电子传输	可见光	TEOA		[50]

图15 （a）ZIS、（b）FS和（c）FS@ZIS-30的SEM图像；（d）FS@ZIS-30的TEM和（e）HRTEM图像；在AM 1.5G照射下，光热辅助光催化析氢实际反应过程中（f）FS@ZIS-30和（g）ZIS样品的温度分布图[56]

Fig.15 The SEM images of (a) ZIS, (b) FS and (c) FS@ZIS-30; (d) TEM and (e) HRTEM images of FS@ZIS-30; The temperature mapping images under AM 1.5G irradiation in the real reaction processes of photothermal-assisted photocatalytic H2 evolution for (f) FS@ZIS-30 and (g) ZIS samples[56]

图16 （a）ZnCdS和（b-d）MoS2的的SEM图像。（e-f）MoS2的TEM和HRTEM图像，（g-h）10% M/ZCS的TEM和HRTEM图像[57]

Fig.16 SEM images of (a) ZnCdS and (b-d) MoS2. TEM and HRTEM images of (e-f) MoS2, (g-h) 10wt% M/ZCS[57]

图17 （a, b）ut-MoS2/ZIS的TEM图像；（c）MoS2的UV-vis吸收光谱[58]

Fig.17 (a, b)TEM images of ut-MoS2/ZIS; (c)UV–vis absorption spectroscopy of MoS2[58]

图18 （a）Mn0.5Cd0.5S和（b）3% Ni-Mn0.5Cd0.5S的SEM图像[60]

Fig.18 SEM images of (a) Mn0.5Cd0.5S and (b) 3wt% Ni –Mn0.5Cd0.5S[60]

图19 ZCM-3样品的（a）SEM，（b）HRTEM图像；（c）析氢反应循环性测试[64]

Fig.19 (a) SEM and (b)HRTEM images of ZCM-3 sample,(c)recyclability of H2 evolution test[64]

图20 CdS-7.5NPO的（a）TEM图像和（b）HRTEM图像；CdS-xNiPOi系列样品的（c）紫外-可见吸收光谱和（d）M-S曲线[65]注:CdS-xNPO series of samples[65]

Fig.20 (a)TEM and (b)HRTEM of CdS-7.5NPO; spectra of (c) UV–Vis absorption and (d) M-S plots of the

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