非金属光敏剂石墨烯量子点与磷化镍耦合用于可见光光催化制氢

doi:10.1016/S1872-2067(18)63135-3

催化学报 ›› 2018, Vol. 39 ›› Issue (11): 1753-1761.DOI: 10.1016/S1872-2067(18)63135-3

非金属光敏剂石墨烯量子点与磷化镍耦合用于可见光光催化制氢

祝亮, 岳秋地, 江道传, 陈涣淋, Rana Muhammad Irfan, 杜平武

中国科学技术大学, 材料科学与工程系, 中国科学院能量转换材料重点实验室, 能源材料化学协同创新中心, 合肥国家微尺度物理实验室, 安徽合肥 230026

收稿日期:2018-06-29 修回日期:2018-07-06 出版日期:2018-11-18 发布日期:2018-09-01
通讯作者: 杜平武
基金资助:
国家重点研发计划（2017YFA0402800）；国家自然科学基金（51772285，21473170）；中央高校基本科研业务费专项资金.

Metal-free graphene quantum dots photosensitizer coupled with nickel phosphide cocatalyst for enhanced photocatalytic hydrogen production in water under visible light

Liang Zhu, Qiudi Yue, Daochuan Jiang, Huanlin Chen, Rana Muhammad Irfan, Pingwu Du

Hefei National Laboratory for Physical Sciences at the Microscale, iChEM(Collaborative Innovation Center of Chemistry for Energy Materials), CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, Anhui, China

Received:2018-06-29 Revised:2018-07-06 Online:2018-11-18 Published:2018-09-01
Contact: 10.1016/S1872-2067(18)63135-3
Supported by:
This work was supported by the National Key Research and Development Program of China (2017YFA0402800), the National Natural Science Foundation of China (51772285, 21473170), and the Fundamental Research Funds for the Central Universities.

摘要/Abstract

摘要：

利用光催化反应制取氢气是满足未来能源可持续利用的一个很有效的方法.然而，如何去开发和利用高效且稳定的非金属光催化剂用于产氢反应是目前所面临的一个巨大的挑战.最近，非金属纳米碳基材料由于其诸多优点而吸引了人们广泛的关注，比如价格低廉、环境友好和良好的稳定性等.另外，石墨烯量子点由于具有很好的水溶性、低毒性，良好的生物兼容性和很好的光学稳定性等优点而被当作是一种能够替代传统量子点的很有前途的材料.除此之外，石墨烯量子点的带隙还可以通过控制其颗粒大小和其表面所带的官能团来进行灵活调控.另一方面，金属磷化物（磷化镍、磷化钴等）已经被证实了是很好的水分解制氢的非贵金属助催化剂，它们可以加快光生电子和空穴的分离，从而提高光催化活性.
本文利用非金属光敏剂石墨烯量子点与非贵金属助催化磷化镍进行耦合制备复合光催化剂，实现了在可见光照射下进行光催化制氢.在最优条件下，复合光催化剂的产氢速率为空白石墨烯量子点的94倍，甚至与在空白量子点上负载1.0 wt% Pt的产氢速率相当.产氢速率的大幅度提升可能是由于在石墨烯的量子点和磷化镍之间形成了半导体-金属接触界面，从而更有效地促进了光生载流子的传输过程.
石墨烯量子点本身有着很好的水溶性，从而利用机械搅拌的方法与磷化镍进行耦合，并在可见光下进行产氢反应.本文采用红外光谱（FTIR）、透射电镜（TEM）、紫外可见光谱（UV-Vis）和荧光光谱（PL）等表征手段研究了空白量子点表面所带的官能团、尺寸大小和光学性能.采用TEM和PL等表征手段来研究复合光催化剂的形貌和产氢性能提高的原因.
对于空白量子点，FTIR结果表明，其表面带有-OH等官能团；TEM结果表明，它的尺寸大小大概在3.6 ±0.5 nm；UV-Vis结果表明，其在可见光区域有着很强的光吸收；PL结果表明，其在波长约为540 nm处有着很强的吸收峰，所对应的带隙约为2.3 eV.对于复合光催化剂，TEM测试结果表明石墨烯量子点在磷化镍上随机分布；从PL结果可见，复合光催化剂的荧光强度明显降低，说明了光生电子从量子点到磷化镍的有效转移，这也是光催化活性提高的重要原因.

关键词: 非贵金属, 光催化, 产氢, 石墨烯量子点, 磷化镍

Abstract:

Photocatalytic hydrogen (H₂) evolution is a promising approach for future sustainable energy utilization. However, it is still a great challenge to develop efficient and stable metal-free photocatalysts with broadband solar absorption in the visible region for H₂ production. Metal-free graphene quantum dot (GQD) is an emerging candidate for this purpose because of its good water-solubility and tunable band gap. On the other hand, metal phosphides (Ni₂P, Co₂P, etc) have been demonstrated as novel noble-metal-free cocatalysts for water splitting, which can efficiently separate electron-hole pairs and enhance the photocatalytic activities. Herein, we report for the first time on the use of OH-functionalized GQDs (OH-GQDs) photosensitizer coupled with Ni₂P nanoparticles for photocatalytic H₂ production with λ > 420 nm light. The H₂ production rate is~94 times higher than that of bare OH-GQDs, which is even comparable to that of OH-GQDs with 1.0 wt% Pt cocatalyst. This enhancement is probably due to the semiconductor-cocatalyst interface interaction between Ni₂P and OH-GQDs to facilitate efficient charge transfer process.

Key words: Noble-metal-free, Photocatalysis, Hydrogen production, OH-functionalized graphene quantum dotts, Ni₂P

祝亮, 岳秋地, 江道传, 陈涣淋, Rana Muhammad Irfan, 杜平武. 非金属光敏剂石墨烯量子点与磷化镍耦合用于可见光光催化制氢[J]. 催化学报, 2018, 39(11): 1753-1761.

Liang Zhu, Qiudi Yue, Daochuan Jiang, Huanlin Chen, Rana Muhammad Irfan, Pingwu Du. Metal-free graphene quantum dots photosensitizer coupled with nickel phosphide cocatalyst for enhanced photocatalytic hydrogen production in water under visible light[J]. Chinese Journal of Catalysis, 2018, 39(11): 1753-1761.

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非金属光敏剂石墨烯量子点与磷化镍耦合用于可见光光催化制氢

Metal-free graphene quantum dots photosensitizer coupled with nickel phosphide cocatalyst for enhanced photocatalytic hydrogen production in water under visible light

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