超薄Ni掺杂ZnIn2S4纳米片用于光催化醇裂解同时制备C-C耦合产物及氢气

doi:10.1016/S1872-2067(21)63931-1

催化学报 ›› 2022, Vol. 43 ›› Issue (4): 1084-1091.DOI: 10.1016/S1872-2067(21)63931-1

超薄Ni掺杂ZnIn₂S₄纳米片用于光催化醇裂解同时制备C-C耦合产物及氢气

李婧宇, 祁明雨, 徐艺军^*()

福州大学化学学院, 能源与环境光催化国家重点实验室, 福建福州350116

收稿日期:2021-07-14 接受日期:2021-07-14 出版日期:2022-03-05 发布日期:2022-03-01
通讯作者: 徐艺军
基金资助:
国家自然科学基金(22172030);国家自然科学基金(22072023);国家自然科学基金(21872029);国家自然科学基金(U1463204);国家万人计划科技创新领军人才(00387072);福建省首批青年拔尖创新人才;福建省高校领军人才;闽江学者特聘教授奖励计划;福建省自然科学基金(2017J07002);福建省自然科学基金(2019J0106)

Efficient splitting of alcohols into hydrogen and C-C coupled products over ultrathin Ni-doped ZnIn₂S₄ nanosheet photocatalyst

Jing-Yu Li, Ming-Yu Qi, Yi-Jun Xu^*()

State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350116, Fujian, China

Received:2021-07-14 Accepted:2021-07-14 Online:2022-03-05 Published:2022-03-01
Contact: Yi-Jun Xu
Supported by:
Natural Science Foundation of China(22172030);Natural Science Foundation of China(22072023);Natural Science Foundation of China(21872029);Natural Science Foundation of China(U1463204);Program for National Science and Technology Innovation Leading Talents(00387072);1st Program of Fujian Province for Top Creative Young Talents;Program for Leading Talents of Fujian Universities;Award Program for Minjiang Scholar Professorship;Natural Science Foundation of Fujian Province(2017J07002);Natural Science Foundation of Fujian Province(2019J0106)

摘要/Abstract

摘要：

光催化析氢技术被认为是解决化石能源紧缺和环境污染问题的有效途径之一. 在传统的光解水体系中, 析氧半反应因涉及到复杂的四电子转移和O=O双键形成, 成为光催化水分解的决速步骤. 光生空穴牺牲试剂的引入虽然可以在一定程度上提高体系的光催化效率, 但同时造成了光生空穴氧化能力的浪费, 且增加了系统成本. 相比之下, 构建由光催化析氢和选择性有机合成相结合的双功能反应平台, 能够同时利用光生电子和空穴获得绿色的清洁燃料和高值化学品, 为解决上述问题提供了一条理想途径.
近年来, 苯甲醇等生物质衍生物平台分子的光催化选择性氧化引起了人们的广泛关注. 研究表明, ZnIn₂S₄可以实现从苯甲醇到C-C耦合产物的选择性光催化脱氢氧化. 然而, 由于光生载流子的快速复合, 单独ZnIn₂S₄的光催化性能往往受到严重抑制. 目前已有一些研究利用将ZnIn₂S₄与合适的助催化剂或与其能级位置匹配的半导体复合等方法构建异质结构, 致力于提高光生载流子的分离和迁移能力. 虽然氢气的产率以及苯甲醇的转化率在复合光催化剂上明显提高, 但体系对液相产物的选择性却由原本的C-C耦合产物变为苯甲醛. 因此, 构建高效且对C-C耦合产物具有高选择性的苯甲醇氧化同时产氢的双功能光催化反应体系仍面临诸多挑战.
本文采用一锅油浴法制备了过渡金属Ni掺杂的超薄ZnIn₂S₄纳米片(ZIS/Ni). 该复合材料可以有效利用太阳能催化一系列芳香醇选择性脱氢偶联, 同时获得清洁的氢气能源以及增值的C-C耦合产物. Ni的掺杂显著提高了ZnIn₂S₄纳米片的光催化性能, 且当Ni掺杂摩尔比为1%时, 复合材料具有最佳的催化活性. 循环活性实验以及反应前后的晶相测试结果表明, 二元复合材料具有良好的光催化稳定性. 研究表明, ZIS/Ni纳米片光催化活性的显著提高主要归因于其优化的电子结构能够有效促进材料光捕获及光生载流子分离转移能力. 另外, 采用电子自旋共振光谱技术对反应过程中的自由基中间体进行原位监测发现,^•CH(OH)Ph是光催化氧化还原过程中关键的自由基中间体.
本研究有望为进一步优化探索新型高效的光催化氧化还原平台, 以绿色可持续的方式, 为同时获得清洁的太阳能燃料和高附加值的化学品提供启发.

关键词: 光催化氧化还原, 镍掺杂, ZnIn₂S₄纳米片, C-C键偶联, 析氢

Abstract:

Integrating selective organic synthesis with hydrogen (H₂) evolution in one photocatalytic redox reaction system sheds light on the underlying approach for concurrent employment of photogenerated electrons and holes towards efficient production of solar fuels and chemicals. In this work, a facile one-pot oil bath method has been proposed to fabricate a noble metal-free ultrathin Ni-doped ZnIn₂S₄ (ZIS/Ni) composite nanosheet for effective solar-driven selective dehydrocoupling of benzyl alcohol into value-added C-C coupled hydrobenzoin and H₂ fuel, which exhibits higher performance than pure ZIS nanosheet. The remarkably improved photoredox activity of ZIS/Ni is mainly attributed to the optimized electron structure featuring narrower band gap and suitable energy band position, which facilitates the ability of light harvesting and photoexcited charge carrier separation and transfer. Furthermore, it has been demonstrated that it is feasible to employ ZIS/Ni for various aromatic alcohols dehydrocoupling to the corresponding C-C coupled products. It is expected that this work can stimulate further interest on the establishment of innovative photocatalytic redox platform coupling clean solar fuels synthesis and selective organic conversion in a sustainable manner.

Key words: Redox photocatalysis, Ni doping, ZnIn₂S₄ nanosheet, C-C coupling, Hydrogen production

李婧宇, 祁明雨, 徐艺军. 超薄Ni掺杂ZnIn₂S₄纳米片用于光催化醇裂解同时制备C-C耦合产物及氢气[J]. 催化学报, 2022, 43(4): 1084-1091.

Jing-Yu Li, Ming-Yu Qi, Yi-Jun Xu. Efficient splitting of alcohols into hydrogen and C-C coupled products over ultrathin Ni-doped ZnIn₂S₄ nanosheet photocatalyst[J]. Chinese Journal of Catalysis, 2022, 43(4): 1084-1091.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63931-1

https://www.cjcatal.com/CN/Y2022/V43/I4/1084

图/表 6

Fig. 1. (a) The schematic illustration for the synthesis of the composite ZIS/Ni NSs via a facile one-pot oil bath method; the SEM images of the pure ZIS NSs (b) and composite ZIS/Ni NSs (c); TEM (d) and HRTEM (e) images of composite ZIS/Ni NSs; (f) the AFM image of ZIS/Ni NSs; (g) The high angle annular dark field (HAADF)-scanning transmission electron microscopy and EDX elemental mapping results of the composite ZIS/Ni NSs. The insets of (e) and (f) are the SAED result and the height profile of composite ZIS/Ni NSs, respectively.

Fig. 2. The XRD patterns (a) and DRS spectra (b) of ultrathin ZIS NSs and ZIS/Ni composite; The high-resolution XPS spectra of Zn 2p (c), In 3d (d), S 2p (e) and Ni 2p (f) of the pure ZIS NSs (bottom) and composite ZIS/Ni NSs (top).

Fig. 3. (a) The illustration for photocatalytic selective oxidation of BA coupling with H2 evolution; (b) The photocatalytic activities of H2 evolution and dehydrocoupling of BA into HB over pure ZIS and ZIS/Nix composites; (c) The conversion of BA and the selectivity to HB over different photocatalysts; Long-time experiments (d) and photocatalytic cyclic tests (e) over ZIS/Ni1 NSs. Reaction conditions: 5 mg photocatalysts in 5 mL CH3CN containing 76.9 μmol BA, irradiation for 2 h.

Table 1 Photocatalytic dehydrocoupling of aromatic alcohols into substituted HB and H2 evolution a.

Entry	-R	H₂ yield (μmol)	Liquid yield (μmol)		Substituted HB selectivity^b(%)	Aromatic alcohols conversion^c(%)	e^-/h^+d
Entry	-R	H₂ yield (μmol)	Substituted HB	By-products	Substituted HB selectivity^b(%)	Aromatic alcohols conversion^c(%)	e^-/h^+d
1	-H	41.9	32.9	0.8	98.5	86.0	1.2
2^e	-H	13.8	16.8	0.6	98.0	46.1	0.8
3^f	-H	19.8	20.5	0.7	97.9	55.6	0.9
4^g	-H	22.5	16.8	7.5	81.8	50.8	0.9
5	-F	32.1	28.5	3.5	93.8	83.5	1.0
6	-Cl	29.1	31.7	0.5	99.2	90.2	0.9
7	-CH₃	37.1	32.6	3.2	95.3	90.4	1.0

Fig. 4. (a) The EPR spectra of pure ZIS and ZIS/Ni1 composites with irradiation for 10 min; (b) The decay curves of photo voltage and electron lifetime of pure ZIS and ZIS/Ni1 composites (see experimental section in supporting information for the calculation formula); The EIS Nyquist plots (c), transient photocurrent responses (d) and time-resolved PL spectra decay curve (e) (λex = 360 nm) of pure ZIS and ZIS/Ni1 composites.

Fig. 5. Illustration of the band structure for ZIS and ZIS/Ni1 composites and the plausible reaction mechanism for photocatalytic selective oxidation of BA coupling with H2 evolution.

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超薄Ni掺杂ZnIn₂S₄纳米片用于光催化醇裂解同时制备C-C耦合产物及氢气

Efficient splitting of alcohols into hydrogen and C-C coupled products over ultrathin Ni-doped ZnIn₂S₄ nanosheet photocatalyst

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