Photocatalytic CO<sub>2</sub> Reduction Using Ni<sub>2</sub>P Nanosheets

Citation: Pan Zhiming, Liu Minghui, Niu Pingping, Guo Fangsong, Fu Xianzhi, Wang Xinchen. Photocatalytic CO₂ Reduction Using Ni₂P Nanosheets[J]. Acta Physico-Chimica Sinica, 2020, 36(1): 190601. doi: 10.3866/PKU.WHXB201906014 shu

Ni₂P纳米片用于光催化二氧化碳还原

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福州大学化学学院，能源与环境光催化国家重点实验室，福州 350116

通讯作者: 王心晨, xcwang@fzu.edu.cn

基金项目:
国家重点研发计划 2018YFA0209301

国家重点研发计划(2018YFA0209301)，长江学者奖励计划(T2016147)，国家自然科学基金(21425309, 21761132002, 21861130353)和111引智计划(D16008)资助项目

长江学者奖励计划 T2016147

国家自然科学基金 21425309

国家自然科学基金 21861130353

国家自然科学基金 21761132002

111引智计划 D16008

摘要: 光催化还原二氧化碳是人工光合作用的重要组成部分，但由于还原二氧化碳的活化能过高导致其应用受到极大地限制。这里，我们报道Ni₂P材料耦合光敏剂能够实现高效的光催化二氧化碳还原。此外，为了进一步的提高二氧化碳还原性能，一种合成超薄片层结构Ni₂P纳米片的策略被采用，目的提高其对二氧化碳吸附能力和降低二氧化碳还原的活化能。一系列物理化学表征被实施，比如X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)和原子力显微镜(AFM)等。这些实验结果证实了厚度为1.5 nm的超薄Ni₂P纳米片被成功地制备。荧光实验结果揭示了Ni₂P纳米片能够更高效地促进光生载流子的分离。此外，电化学实验证明了Ni₂P纳米片具有较高的活性比表面积和电荷导电性，因此可以为二氧化碳转化提供更多的活性中心，从而加快其界面反应动力学。光催化二氧化碳还原实验结果展现了Ni₂P纳米片光催化一氧化碳的生成速率为64.8 μmol·h^-1，且其活性是Ni₂P颗粒光催化二氧化碳还原活性的四倍，同时它展现出较高化学稳定性。这项工作为超薄Ni₂P纳米片在光催化二氧化碳中的应用提供了新的思路。

关键词:

English

Photocatalytic CO₂ Reduction Using Ni₂P Nanosheets

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

Corresponding author: Wang Xinchen, xcwang@fzu.edu.cn

Received Date: 04 June 2019
Accepted Date: 11 July 2019
Revised Date: 05 July 2019
Available Online: 15 January 2020
Fund Project:

The project was supported by the National Key Technology R&D Program of China (2018YFA0209301), the Chang Jiang Scholars Program of China (T2016147), the National Natural Science Foundation of China (21425309, 21761132002, 21861130353) and the 111 Project, China (D16008)

Abstract: Artificial photosynthesis is an ideal method for solar-to-chemical energy conversion, wherein solar energy is stored in the form of chemical bonds of solar fuels. In particular, the photocatalytic reduction of CO₂ has attracted considerable attention due to its dual benefits of fossil fuel production and CO₂ pollution reduction. However, CO₂ is a comparatively stable molecule and its photoreduction is thermodynamically and kinetically challenging. Thus, the photocatalytic efficiency of CO₂ reduction is far below the level of industrial applications. Therefore, development of low-cost cocatalysts is crucial for significantly decreasing the activation energy of CO₂ to achieving efficient photocatalytic CO₂ reduction. Herein, we have reported the use of a Ni₂P material that can serve as a robust cocatalyst by cooperating with a photosensitizer for the photoconversion of CO₂. An effective strategy for engineering Ni₂P in an ultrathin layered structure has been proposed to improve the CO₂ adsorption capability and decrease the CO₂ activation energy, resulting in efficient CO₂ reduction. A series of physicochemical characterizations including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and atomic force microscopy (AFM) were used to demonstrate the successful preparation of ultrathin Ni₂P nanosheets. The XRD and XPS results confirm the successful synthesis of Ni₂P from Ni(OH)₂ by a low temperature phosphidation process. According to the TEM images, the prepared Ni₂P nanosheets exhibit a 2D and near-transparent sheet-like structure, suggesting their ultrathin thickness. The AFM images further demonstrated this result and also showed that the height of the Ni₂P nanosheets is ca 1.5 nm. The photoluminescence (PL) spectroscopy results revealed that the Ni₂P material could efficiently promote the separation of the photogenerated electrons and holes in [Ru(bpy)₃]Cl₂·6H₂O. More importantly, the Ni₂P nanosheets could more efficiently promote the charge transfer and charge separation rate of [Ru(bpy)₃]Cl₂·6H₂O compared with the Ni₂P particles. In addition, the electrochemical experiments revealed that the Ni₂P nanosheets, with their high active surface area and charge conductivity, can provide more active centers for CO₂ conversion and accelerate the interfacial reaction dynamics. These results strongly suggest that the Ni₂P nanosheets are a promising material for photocatalytic CO₂ reduction, and can achieve a CO generation rate of 64.8 μmol·h^-1, which is 4.4 times higher than that of the Ni₂P particles. In addition, the XRD and XPS measurements of the used Ni₂P nanosheets after the six cycles of the photocatalytic CO₂ reduction reaction demonstrated their high stability. Overall, this study offers a new function for the 2D transition-metal phosphide catalysts in photocatalytic CO₂ reduction.

Key words:

Photocatalysis
/ Nanosheet
/ Ni₂P
/ CO₂ reduction
/ CO

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Ni₂P纳米片用于光催化二氧化碳还原

通讯作者: 王心晨, xcwang@fzu.edu.cn

English

Photocatalytic CO₂ Reduction Using Ni₂P Nanosheets

Corresponding author: Wang Xinchen, xcwang@fzu.edu.cn

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Ni2P纳米片用于光催化二氧化碳还原

通讯作者: 王心晨, xcwang@fzu.edu.cn

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Corresponding author: Wang Xinchen, xcwang@fzu.edu.cn

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