黑磷的液相法制备研究进展

doi:10.19964/j.issn.1006-4990.2021-0311

摘要/Abstract

摘要：

黑磷因其独特的结构和优异的性能在许多领域展现出很好的应用前景。目前黑磷的应用仍受限于其制备方法及剥离方法。液相法是在液相条件下合成黑磷的方法,主要包括汞回流法、铋熔化法和溶剂热法。液相法可以一步制备出纳米黑磷,具有操作简单、反应条件温和、可控性强等优点,是目前最有可能实现纳米黑磷的低成本、可控制备的方法。综述了液相法制备黑磷的研究现状,分析并讨论了该方法的优点和不足之处。针对液相法制备出的黑磷存在晶型差、产率低且不稳定的问题,提出选择合适的溶剂、调控反应温度有望制备出新型结构的纳米黑磷基材料并提高黑磷的结晶性及产率,同时在制备过程中实现原位掺杂或形成复合材料有望提升黑磷的稳定性,进而拓宽黑磷的应用领域并提升黑磷的性能。

关键词: 黑磷, 液相法, 汞回流法, 铋熔化法, 溶剂热法

Abstract:

Because of its unique structure and excellent performance,black phosphorus has performed good application prospects in many fields.At present,the application of black phosphorus is still limited by its preparation methods and stripping methods.Liquid phase method is a method of synthesizing black phosphorus under liquid phase conditions,mainly including mercury reflux method,bismuth melting method and solvent thermal method.Liquid phase method can prepare nano black phosphorus in one step,which has the advantages of simple operation,mild reaction conditions and strong controllabi-lity.It is the most likely method to realize the low-cost and controllable preparation of nano black phosphorus at present.The research status of preparation of black phosphorus by liquid phase method was reviewed.The advantages and disadvantages of this method were analyzed and discussed.In view of the problems of poor crystallinity,low yield and instability of the black phosphorus prepared by this method,it was proposed that choosing appropriate solvent and adjusting reaction temperature were expected to prepare a new structure of nano black phosphorous based materials and improve the crystallinity and yield of black phosphorous.At the same time,in the preparation process to achieve in situ doping or formation of composite materials were expected to improve the stability of black phosphorous,and then broadened the application field of black phosphorous and improved the performance of black phosphorous.

Key words: black phosphorus, liquid phase method, mercury reflux method, bismuth melting method, solvothermal method

中图分类号:

TQ126.31

卢晓敏,李雪梅,刘岚君,沈晓芳,梅毅,廉培超. 黑磷的液相法制备研究进展[J]. 无机盐工业, 2022, 54(3): 31-37.

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.

图/表 11

图1

图2

图3

图4

图5

图6

图7

表1

图8

图9

图10

参考文献 27

[1]	BRIDGMAN P W. Two new modifications of phosphorus[J]. Journal of the American Chemical Society, 1914, 36(7):1344-l363.
[2]	BRENT J R, SAVJANI N, LEWIS E A, et al. Production of few-layer phosphorene by liquid exfoliation of black phosphorus[J]. Chemical Communications, 2014, 50(87):13338-13341.
[3]	QIAO J S, KONG X H, HU Z X, et al. High-mobility transport aniso-tropy and linear dichroism in few-layer black phosphorus[J]. Nature Communications, 2014, 5.Doi: 10.1038/ncomms5475.
[4]	JIN H C, XIN S, CHUANG C H, et al. Black phosphorus composites with engineered interfaces for high-rate high-capacity lithium stor-age[J]. Science, 2020, 370(6513):192-197.
[5]	ZHANG K, JIN B J, PARK C, et al. Black phosphorene as a hole ex-traction layer boosting solar water splitting of oxygen evolution cat-alysts[J]. Nature Communications, 2019, 10(1).Doi: 10.1038/s41467-019-10034-1.
[6]	LI L K, YU Y J, YE G J, et al. Black phosphorus field-effect transis-tors[J]. Nature Nanotechnology, 2014, 9(5):372-377.
[7]	YANG Y, GAO J, ZHANG Z, et al. Black phosphorus based photoca-thodes in wideband bifacial dye-sensitized solar cells[J]. Advanced Materials, 2016, 28(40):8937-8944.
[8]	REN X L, MEI Y, LIAN P C, et al. A novel application of phospho-rene as a flame retardant[J]. Polymers, 2018, 10(3).Doi: 10.3390/polym10030227.
[9]	QU G B, XIA T, ZHOU W H, et al. Property-activity relationship of black phosphorus at the nano-bio interface:From molecules to orga-nisms[J]. Chemical Reviews, 2020, 120(4):2288-2346.
[10]	BRIDGMAN P W. Reversible transitions between solids at high pressures[J]. Physical Review, 1914, 3(6).Doi: 10.1103/PhysRev.3.489.
[11]	LANGE S, SCHMIDT P, NILGES T. Au₃SnP₇@black phosphorus:An easy access to black phosphorus[J]. Inorganic Chemistry, 2007, 46(10):4028-4035.
[12]	PARK C M, SOHN H J. Black phosphorus and its composite for li-thium rechargeable batteries[J]. Advanced Materials, 2007, 19(18):2465-2468.
[13]	KREBS H, SCHULTZE-GEBHARDT F. Über die struktur und ei-genschaften der halbmetalle.Ⅶ.neubestimmung der struktur des glasigen selens nach verbesserten röntgenographischen metho-den[J]. Acta Crystallographica, 1955, 8(7):412-419.
[14]	BROWN A, RUNDQVIST S. Refinement of the crystal structure of black phosphorus[J]. Acta Crystallographica, 1965, 19(4):684-685.
[15]	TIAN B, SMITH B, SCOR M, et al. Facile bottom-up synjournal of partially oxidized black phosphorus nanosheets as metal-free pho-tocatalyst for hydrogen evolution[J]. Proceedings of the National Academy of Sciences of the United States of America, 2018, 115(17):4345-4350.
[16]	MARUYAMA Y, SUZUKI S, KOBAYASHI K, et al. Synjournal and some properties of black phosphorus single crystals[J]. Physica B+C, 1981, 105(1):99-102.
[17]	BABA M, IZUMIDA F, TAKEDA Y, et al. Preparation of black pho-sphorus single crystals by a completely closed bismuth-flux method and their crystal morphology[J]. Japanese Journal of Applied Phy-sics, 1989, 28(6):1019-1022.
[18]	刘红红, 陆艳, 张文强, 等. 纳米黑磷制备的研究进展[J]. 磷肥与复肥, 2018, 33(1):26-31.
[19]	LI Y, JIANG S, QIAN Y, et al. Amine-induced phase transition from white phosphorus to red/black phosphorus for Li/K-ion stor-age[J]. Chemical Communications, 2019, 55(47):6751-6754.
[20]	LIU F L, SHI R, WANG Z, et al. Direct Z-scheme hetero-phase ju-nction of black/red phosphorus for photocatalytic water splitting[J]. Angewandte Chemie:International Edition, 2019, 58(34):11791-11795.
[21]	ZHU S T, LIANG Q S, XU Y T, et al. Facile solvothermal synjournal of black phosphorus nanosheets from red phosphorus for efficient photocatalytic hydrogen evolution[J]. European Journal of Inor-ganic Chemistry, 2020, 2020(9):773-779.
[22]	WANG Y, HE M X, MA S B, et al. Low-temperature solution syn-journal of black phosphorus from red phosphorus:Crystallization mechanism and lithium ion battery applications[J]. Journal of Phy-sical Chemistry Letters, 2020, 11(7):2708-2716.
[23]	OZAWA A, YAMAMOTO M, TANABE T, et al. Black phosphorus synthesized by solvothermal reaction from red phosphorus and its catalytic activity for water splitting[J]. Journal of Materials Chemi-stry A, 2020, 8(15):7368-7376.
[24]	LIU Y Q, HE L D, LIAN P C. Progress on stability enhancement of black phosphorene[J]. CIESC Journal, 2020, 71(3):936-944.
[25]	LIU H H, LIAN P C, TANG Y W, et al. Facile synjournal of an air-stable 3D reduced graphene oxide-phosphorene composite by so-nication[J]. Applied Surface Science, 2019, 476:972-981.
[26]	ZHAO G, WANG T L, SHAO Y L, et al. A novel mild phase-transi-tion to prepare black phosphorus nanosheets with excellent energy applications[J]. Small, 2017, 13(7).Doi: 10.1002/smll.201602243.
[27]	ZHANG Y Y, RUI X H, TANG Y X, et al. Wet-chemical process-ing of phosphorus composite nanosheets for high-rate and high-ca-pacity lithium-ion batteries[J]. Advanced Energy Materials, 2016, 6(10).Doi: 10.1002/aenm.201502409.

样品	T/℃	t/h	d（红磷）/μm	ρ（红磷）/（g·L^-1）	带隙/eV	I（红磷）/a.u.^[a]	I（黑磷）/a.u.^[b]	I（黑磷）/I（红磷+黑磷）/%	d（黑磷晶体）/nm
1	140	12	23	15	1.88	397	14	3.3	—
2	150	12	23	15	1.56	288	35	10.7	—
3	160	12	23	15	1.55	183	108	37.2	68（17）
4	170	12	23	15	1.55	165	63	27.7	—
5	160	12	23	15	1.55	190	108	36.3	68（17）
6	160	24	23	15	1.55	190	280	59.6	298（16）
7	160	48	23	15	1.55	211	176	45.4	109（10）
8	160	24	23	15	1.55	142	280	66.3	298（16）
9	160	24	68	15	1.55	29	542	94.9	195（10）
10	160	24	1 300	15	1.88	247	3	1.2	—
11	160	24	68	3.75	1.60	222	9	3.8	—
12	160	24	68	7.5	1.60	176	101	36.5	178（7）
13	160	24	68	15	1.55	29	542	94.9	195（8）
14	160	24	68	30	1.56	18	551	96.8	219（7）

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会