磷化法制备Ni x P y 及其复合材料光解水性能

doi:10.16085/j.issn.1000-6613.2021-0989

化工进展 ›› 2022, Vol. 41 ›› Issue (5): 2468-2475.DOI: 10.16085/j.issn.1000-6613.2021-0989

磷化法制备Ni _x P _y 及其复合材料光解水性能

颜瑞¹^,²(), 孙志超¹^,²(), 张蒙蒙¹^,², 刘颖雅¹^,², 遇治权¹^,², 王伟³, 王瑶¹^,², 王安杰¹^,²

^1.大连理工大学精细化工国家重点实验室，辽宁大连 116024
^2.辽宁省高校石油化工技术与装备重点实验室，辽宁大连 116024
^3.银川能源学院，宁夏银川 750105

收稿日期:2021-05-11 修回日期:2021-11-16 出版日期:2022-05-05 发布日期:2022-05-24
通讯作者: 孙志超
作者简介:颜瑞（1996—），男，硕士研究生，研究方向为NixPy的制备及光催化性能。E-mail: yanrui96@126.com。
基金资助:
国家重点研发计划政府间国际科技创新合作重点专项(2016YFE0109800);国家自然科学基金(21603024);辽宁省博士启动基金(201601038);宁夏重点研发计划(2018BEE03030);中央高校基本科研业务费项目(DUT19GJ205)

Photocatalytic properties of Ni _x P _y and its composites prepared by phosphating method

YAN Rui¹^,²(), SUN Zhichao¹^,²(), ZHANG Mengmeng¹^,², LIU Yingya¹^,², YU Zhiquan¹^,², WANG Wei³, WANG Yao¹^,², WANG Anjie¹^,²

^1.State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, Liaoning, China
^2.Liaoning Key Laboratory of Petrochemical Technology and Experiment, Dalian 116024, Liaoning, China
^3.Yinchuan Energy Institute, Yinchuan 750105, Ningxia, China

Received:2021-05-11 Revised:2021-11-16 Online:2022-05-05 Published:2022-05-24
Contact: SUN Zhichao

摘要/Abstract

摘要：

磷化镍具有Ni₃P、Ni₁₂P₅、Ni₂P、Ni₅P₄等多种晶相，深入研究各个晶相的制备规律和稳定存在条件对开发磷化镍基催化材料至关重要。本文系统考察了磷化时间、磷化温度、Ni/P摩尔比、磷化气速和磷源种类对制备晶相的影响。结果发现，以Ni₃P为前体、红磷为磷源时，可以得到Ni₅P₄、Ni₂P、Ni₁₂P₅三种晶相；以次磷酸盐为磷源时只能得到Ni₂P和Ni₁₂P₅晶相。当以红磷为磷源时，反应温度是影响晶相的主要因素，磷化温度为500℃、600℃和800℃时分别得到Ni₅P₄、Ni₂P和Ni₁₂P₅晶相。将制备的Ni₃P、Ni₂P、Ni₁₂P₅和Ni₅P₄作为助剂，与CdS复合制备光催化复合材料，得到的4种Ni _x P _y /CdS复合材料均表现出良好的光解水制氢性能，Ni₅P₄/CdS表现出最优的产氢能力，为CdS的5.4倍。表征结果证明，引入Ni _x P _y 能够有效抑制反应过程中CdS的载流子复合，提升其光解水反应活性。

关键词: 催化, 复合材料, 光化学, 磷化镍, 晶相, 硫化镉

Abstract:

Nickel phosphide (Ni _x P _y ) has many crystalline phases, such as Ni₃P, Ni₁₂P₅, Ni₂P, Ni₅P₄, etc. It is important to study the preparation rule and stable existence conditions of each crystalline phase for the development of catalysts based on Ni _x P _y . In this paper, the effects of phosphating time, phosphating temperature, Ni/P molar ratio, phosphating gas velocity and phosphorus source on the crystal phase were investigated. The results showed that three crystalline phases of Ni₅P₄, Ni₂P and Ni₁₂P₅ can be obtained with Ni₃P and red phosphorus as precursors. Only Ni₂P and Ni₁₂P₅ crystal phases can be obtained with hypophosphite as phosphorus source. The reaction temperature was the main factor affecting the crystal phase when red phosphorus was used as the phosphorus source. Ni₅P₄, Ni₂P and Ni₁₂P₅crystal phases were obtained at 500℃, 600℃ and 800℃, respectively. Ni₃P, Ni₂P, Ni₁₂P₅ and Ni₅P₄ were used as cocatalysts to prepare photocatalytic composites. All the four cocatalysts of Ni _x P _y can significantly enhance the hydrogen production activity of CdS. Ni₅P₄/CdS indicated the best hydrogen production capacity, which was 5.4 times that of CdS. The results of characterization showed that the introduction of Ni _x P _y could effectively inhibit the carrier recombination and enhance the photocatalytic activity of CdS.

Key words: catalysis, composites, photochemistry, nickel phosphide, crystalline phase, cadmium sulfide

中图分类号:

TQ138.1

颜瑞, 孙志超, 张蒙蒙, 刘颖雅, 遇治权, 王伟, 王瑶, 王安杰. 磷化法制备Ni _x P _y 及其复合材料光解水性能[J]. 化工进展, 2022, 41(5): 2468-2475.

YAN Rui, SUN Zhichao, ZHANG Mengmeng, LIU Yingya, YU Zhiquan, WANG Wei, WANG Yao, WANG Anjie. Photocatalytic properties of Ni _x P _y and its composites prepared by phosphating method[J]. Chemical Industry and Engineering Progress, 2022, 41(5): 2468-2475.

图/表 8

图1 不同磷化温度和磷化时间下制备样品的XRD谱图

图2 不同Ni/P摩尔比和磷化气速下制备样品的XRD谱图

图3 使用次亚磷酸钠作磷源时，不同条件下制备样品的XRD谱图(次亚磷酸钠，500℃, Ni∶P=1∶4, 2h, 20mL/min)

图4 Ni5P4、Ni2P、Ni12P5、Ni3P的XPS谱图

图5 CdS和5 % Ni x P y /CdS复合材料的XRD谱图

图6 CdS和5% Ni x P y /CdS复合材料的UV-vis谱图和PL谱图

图7 CdS和5% Ni x P y /CdS复合材料的制氢速率和5% Ni5P4/CdS循环产氢实验

图8 Ni x P y /CdS复合材料光解水制氢机理示意图

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磷化法制备Ni _x P _y 及其复合材料光解水性能

Photocatalytic properties of Ni _x P _y and its composites prepared by phosphating method

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磷化法制备Ni x P y 及其复合材料光解水性能

Photocatalytic properties of Ni x P y and its composites prepared by phosphating method

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磷化法制备Ni _x P _y 及其复合材料光解水性能

Photocatalytic properties of Ni _x P _y and its composites prepared by phosphating method