NiS2助剂修饰g-C3N4光催化剂的简易合成及光催化制氢性能增强研究

引用本文: 陈峰, 杨慧, 王雪飞, 余火根. NiS₂助剂修饰g-C₃N₄光催化剂的简易合成及光催化制氢性能增强研究[J]. 催化学报, 2017, 38(2): 296-304. doi: 10.1016/S1872-2067(16)62554-8 shu

Citation: Feng Chen, Hui Yang, Xuefei Wang, Huogen Yu. Facile synthesis and enhanced photocatalytic H₂-evolution performance of NiS₂-modified g-C₃N₄ photocatalysts[J]. Chinese Journal of Catalysis, 2017, 38(2): 296-304. doi: 10.1016/S1872-2067(16)62554-8 shu

NiS₂助剂修饰g-C₃N₄光催化剂的简易合成及光催化制氢性能增强研究

陈峰 ^a, ,
杨慧 ^a, ,
王雪飞 ^a, ,
余火根 ^a,b,

a 武汉理工大学化学, 化工与生命科学学院, 湖北武汉 430070;
b 武汉理工大学硅酸盐国家重点实验室, 湖北武汉 430070
基金项目:
国家自然科学基金（21277107，21477094，51672203，51472192）；新世纪优秀人才计划（NCET-13-0944）；中央高校基础研究基金（WUT2015IB002）.

摘要: g-C₃N₄是一种新型的稳定的半导体光催化材料，它可以通过热缩聚法、固相反应法、电化学沉积法和溶剂热法等制备.g-C₃N₄禁带宽度约为2.7 eV，吸收边在460 nm左右，具有合适的导带位置，可用作可见光响应制氢的光催化材料，但在实际应用中g-C₃N₄光催化性能较低，其原因可归纳为：（1）g-C₃N₄在吸收光子产生电子和空穴对后，光生载流子的传输速率较慢，容易在体相或表面复合，致使g-C₃N₄的量子效率较低；（2）材料在合成过程中易于结块，使g-C₃N₄的比表面积远小于理论值，严重削弱了g-C₃N₄光催化材料的制氢性能.目前已有很多关于g-C₃N₄改性的报道，但一些方法对材料的处理过程耗时较长或者合成过程较难控制.用助剂改性是提高光催化制氢活性的半导体材料的主要策略之一.合适的助剂可改进电荷分离和加速表面催化反应，从而提高光催化剂的制氢活性.虽然稀有金属或贵金属，如铂、金和银可大大提高g-C₃N₄的制氢速率，但由于其昂贵和稀缺性，因而应用严重受限.因此，开发成本低、储量丰富、高性能助剂来进一步提高制氢性能具有重要意义.
NiS₂来源丰富、价格低廉.它可在酸性和碱性的环境保持相对较高的稳定性，且其表面电子结构表现出类金属特性.但它较难与半导体光催化剂形成强耦合和界面，通常需要水热等条件下合成.实验表明，g-C₃N₄表面存在着大量的含氧官能团及未缩合的氨基基团，为表面接枝提供了丰富的反应活性位点，因而可利用g-C₃N₄表面均匀分布的含氧官能团等和Ni²⁺结合，再原位与S^2-反应，从而在g-C₃N₄上负载耦合紧密的NiS₂助剂，进一步提高复合材料的光催化制氢活性.
本文采用低温浸渍法制备了NiS₂/g-C₃N₄光催化剂.NiS₂助剂在温和的反应条件下与g-C₃N₄光催化剂复合，可以防止催化剂结构的破坏，同时使得助剂均匀地分散，并紧密结合在催化剂表面，从而大大提高光催化剂的制氢性能.该样品制备过程为：（1）通过水热处理制备含氧官能团和较大比表面积的g-C₃N₄；（2）添加Ni（NO₃）₂前驱体后，Ni²⁺离子由于静电作用紧密吸附在g-C₃N₄表面；（3）在80℃加入硫代乙酰胺（TAA），可在g-C₃N₄的表面紧密和均匀形成助剂NiS₂.表征结果证实成功制备NiS₂纳米粒子修饰的g-C₃N₄光催化剂.当Ni含量为3 wt%，样品表现出最大的制氢速率（116 μmol h^-1 g^-1），明显高于纯g-C₃N₄.此外，对NiS₂/g-C₃N₄（3 wt%）的样品进行光催化性能的循环测试结果表明：该样品在可见光照射下可以保持一个稳定的、有效的光催化制氢性能.根据实验结果，我们提出一个可能的光催化机理：即NiS₂促进了物质表面快速转移光生电子，使g-C₃N₄光生电荷有效分离.基于NiS₂具有成本低和效率高的优点，因而有望广泛应用于制备高性能的光催化材料.

关键词:

English

Facile synthesis and enhanced photocatalytic H₂-evolution performance of NiS₂-modified g-C₃N₄ photocatalysts

a School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070, Hubei, China;
b State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, Hubei, China
Received Date: 30 August 2016
Revised Date: 28 September 2016
Available Online: 02 March 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (21277107, 21477094, 51672203, 51472192), the Program for New Century Excellent Talents in University (NCET-13-0944), and the Fundamental Research Funds for the Central Universities (WUT 2015IB002).

Abstract: NiS₂ is a promising cocatalyst to improve the photocatalytic performance of g-C₃N₄ for the production of H₂. However, the synthesis of the NiS₂ cocatalyst usually requires harsh conditions, which risks destroying the microstructures of the g-C₃N₄ photocatalysts. In this study, a facile and low-temperature (80℃) impregnation method was developed to prepare NiS₂/g-C₃N₄ photocatalysts. First, the g-C₃N₄ powders were processed by the hydrothermal method in order to introduce oxygen-containing functional groups (such as -OH and -CONH-) to the surface of g-C₃N₄. Then, the Ni²⁺ ions could be adsorbed near the g-C₃N₄ via strong electrostatic interaction between g-C₃N₄ and Ni²⁺ ions upon the addition of Ni(NO₃)₂ solution. Finally, NiS₂ nanoparticles were formed on the surface of g-C₃N₄ upon the addition of TAA. It was found that the NiS₂ nanoparticles were solidly and homogeneously grafted on the surface of g-C₃N₄, resulting in greatly improved photocatalytic H₂ production. When the amount of NiS₂ was 3 wt%, the resultant NiS₂/g-C₃N₄ photocatalyst showed the highest H₂ evolution rate (116.343 μmol h^-1 g^-1), which is significantly higher than that of the pure g-C₃N₄ (3 μmol h^-1 g^-1). Moreover, the results of a recycling test for the NiS₂/g-C₃N₄(3 wt%) sample showed that this sample could maintain a stable and effective photocatalytic H₂-evolution performance under visible-light irradiation. Based on the above results, a possible mechanism of the improved photocatalytic performance was proposed for the presented NiS₂/g-C₃N₄ photocatalysts, in which the photogenerated electrons of g-C₃N₄ can be rapidly transferred to the NiS₂ nanoparticles via the close and continuous contact between them; then, the photogenerated electrons rapidly react with H₂O adsorbed on the surface of NiS₂, which has a surficial metallic character and high catalytic activity, to produce H₂. Considering the mild and facile synthesis method, the presented low-cost and highly efficient NiS₂-modified g-C₃N₄ photocatalysts would have great potential for practical use in photocatalytic H₂ production.

Key words:

Photocatalysis
/ NiS₂
/ Graphite-like carbon-nitride
/ Cocatalyst
/ Visible-light photocatalytic hydrogen evolution

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沈阳化工大学材料科学与工程学院沈阳 110142

NiS₂助剂修饰g-C₃N₄光催化剂的简易合成及光催化制氢性能增强研究

English

Facile synthesis and enhanced photocatalytic H₂-evolution performance of NiS₂-modified g-C₃N₄ photocatalysts

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