黑磷制备工艺研究进展

doi:10.19964/j.issn.1006-4990.2024-0319

Abstract

Abstract:

In recent years，as a conceptually new two-dimensional layered material，black phosphorus（BP） has good development potential in semiconductor，electrochemistry，solar cells，photocatalysis，flame retardant，biomedicine and other fields owing to its unique structure and excellent physicochemical properties，such as large specific surface area，high anisotropy，wide light absorption，high carrier mobility.Due to the high cost of black phosphorus，further advancement and application of this material have been hindered，thereby making the research on its synthesis processes become a focus topic.The preparation processes of black phosphorus were reviewed.Firstly，the physicochemical properties of black phosphorus and its application fields were introduced.Subsequently，various synthesis methods were outlined，encompassing high-pressure methods，mechanical ball milling，solvothermal synthesis，bismuth melting process，mercury reflux method，and chemical vapor transport（CVT） method，etc.Particular emphasis was placed on the optimization procedures and mechanism related to CVT.The advantages and disadvantages of each preparation technique were summarized and the future development direction was prospected.

Key words: black phosphorus, two dimensional materials, preparation process, chemical vapor transfer method, mechanism research

CLC Number:

TQ126.3

LI Yongxiang, LIU Chenxi, LI Yundong, MA Hang, MEI Lianping, DANG Hui, SUN Zhi, WAN Banglong. Research progress of preparation technology of black phosphorus[J]. Inorganic Chemicals Industry, 2025, 57(3): 18-29.

Figures/Tables 13

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方法	工艺	优点	缺点
高压法	以红磷或白磷为原料，在高温（200~1 000 ℃）、高压（1.2~4.5 GPa）下制备黑磷	反应时间短（5~60 min），不需要额外催化剂，产品晶型好	压力要求极高、制备出的黑磷尺寸小、产率低
汞催化法	以白磷为原料，引入金属汞作为催化剂，在高温（370~410 ℃）下制备黑磷	无需高压条件、制备成本低、能耗低	汞催化剂难以去除，且具有毒性，制备周期长（数天）
铋熔化法	以白磷为原料，将液态铋浇筑在白磷上，在高温下（400 ℃）制备黑磷	避免了有毒催化剂的使用、产品晶型好	制备工艺复杂、制备周期长（20~58 h）、产品含有杂质，纯度低
机械球磨法	以红磷为原料，利用机械能制备黑磷	工艺操作简单、无副产物产生、无需加入催化剂或溶剂、制备周期短（1~2 h）、易于工业化生产	黑磷产品尺寸小、晶型差、产品含有红磷杂质、纯度低
化学气相传输法	以红磷为原料，固体红磷和矿化剂（Sn、I₂、SnI₂、SnI₄等）在高温区升华，然后以结晶的形式于低温区结晶成黑磷	反应工艺简单、成本低、能耗低、工艺技术较为成熟、晶型好	反应机理不明确、制备周期长（10 h~数天）、产品含有矿化剂等杂质、纯度低

[1]	LU Xiaomin,LI Xuemei,LIU Lanjun,SHEN Xiaofang,MEI Yi,LIAN Peichao. Research progress in preparation of black phosphorus by liquid phase method [J]. Inorganic Chemicals Industry, 2022, 54(3): 31-37.
[2]	LIU Chang,DUAN Zunbin,WANG Jiannan,MA Huijuan,WANG Jiahong,YU Xuefeng. Research progress on new inorganic phosphorus-based flame retardants [J]. Inorganic Chemicals Industry, 2022, 54(11): 8-17.
[3]	Hou Ranran,Cao Changdie,Liu Lanjun,Li Guangneng,Mei Yi,Lian Peichao. Research progress on the preparation of nano-black phosphorus by electrochemical exfoliation from black phosphorus [J]. Inorganic Chemicals Industry, 2021, 53(6): 95-100.
[4]	Jiang Yuncai,Li Xuemei,Wu Zhaoxian,Cao Changdie,Mei Yi,Lian Peichao. Research progress on preparation and application in energy storage of black phosphorus [J]. Inorganic Chemicals Industry, 2021, 53(6): 59-71.
[5]	Ye Weihui,Lü Qi,Long Changjiang. Study on rapid preparation process of high-density spherical basic nickel carbonate [J]. Inorganic Chemicals Industry, 2021, 53(5): 69-72.
[6]	Yang Huanhuan,Yu Binlu,Wang Jiahong,Yu Xuefeng. Preparation,surface functionalization and photoelectrocatalysis of two-dimensional black phosphorus [J]. Inorganic Chemicals Industry, 2021, 53(5): 13-20.
[7]	Wang Xiheng,Sun Wenzhe,Zhang Ling. Research progress in production process of silicon tetrafluoride [J]. Inorganic Chemicals Industry, 2020, 52(1): 35-38.

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Research progress of preparation technology of black phosphorus

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