Research progress on preparation of low-dimensional black phosphorus and its applications in photodegradation field

doi:10.16085/j.issn.1000-6613.2020-0667

Abstract

Abstract:

Low-dimensional black phosphorus plays an indispensable role in the field of photocatalytic degradation due to its numerous advantages, such as directly adjustable bandgap structure, high carrier mobility, and good biocompatibility, etc. However, it is sensitively oxidized under the ambient environment and electron-hole pairs are rapidly recombined, leading to low utilization rate. Therefore, to prepare the stable and efficient low-dimensional black phosphorus composites is significant for its practical applications. In this paper, the preparation of low-dimensional black phosphorus and the application of its composite in the photodegradation field were reviewed. The exfoliation effects and changes in optical properties of low-dimensional black phosphorus prepared via different methods were compared. Mechanical exfoliate methods, chemical vapor deposition methods, liquid exfoliate methods, and solvent thermal synthesis methods were described in detail. The composite materials of carbon, metal, semiconductor, and other materials as well as composites prepared by low-dimensional black phosphorus were summarized. The activities of the composites in the field of photodegradation and the optical changes of low-dimensional black phosphor composites were analyzed. The problems existing in the preparation of low-dimensional black phosphorus and its composites were presented. Through the different preparation methods of composites described in this paper, its practical applications were put forward.

Key words: black phosphorus, nanomaterials, composites, photocatalyst, photodegradation

摘要：

低维黑磷具有直接可调节带隙结构、高载流子迁移率及良好的生物相容性等优点，使其在光催化降解领域有着不可或缺的地位，但它存在自然环境下极易被氧化和电子空穴利用率低等问题。制备稳定且高效的低维黑磷复合材料对于其实际应用有着重要的意义。本文介绍了低维黑磷的制备和低维黑磷复合材料在光催化降解领域的应用。对不同方法制备的低维黑磷的效果和光学性质的改变进行了比较，对机械剥离、化学气相沉积、液相剥离和溶剂热合成法进行了详细描述及总结。结合现有文献，对碳质、金属、半导体及其他材料和低维黑磷制备的复合材料进行了总结，并对复合材料在光催化降解领域的效果和复合后低维黑磷光学性质的改变进行了分析。提出了低维黑磷及其复合材料在制备上存在的问题，通过文中所述的复合方法及所选复合材料，对低维黑磷的实际应用进行了展望。

关键词: 黑磷, 纳米材料, 复合材料, 光催化剂, 光催化降解

CLC Number:

TQ126.3

Yizun LIANG, Yanqing GE, Chi WANG, Kai LI, Yi MEI. Research progress on preparation of low-dimensional black phosphorus and its applications in photodegradation field[J]. Chemical Industry and Engineering Progress, 2021, 40(2): 845-858.

梁一尊, 葛艳清, 王驰, 李凯, 梅毅. 低维黑磷的制备及其在光催化降解领域的应用研究进展[J]. 化工进展, 2021, 40(2): 845-858.

Figures/Tables 20

制备方法	平均尺寸	参考文献
少层黑磷烯
机械剥离：使用胶带粘撕	5nm	[9]
机械剥离：使用胶带粘撕	0.85nm	[22]
CVD：将红磷放置于SiO₂衬底上生长	10~20nm	[24]
CVD：将红磷放置于聚酯纤维衬底上生长	40nm	[25]
液相剥离：NMP作为溶剂，超声波清洗器处理24h	3.5~5nm	[26]
液相剥离：NMP中添加NaOH，在12000r/min的条件下离心	3.5nm±2nm	[27]
液相剥离：OTF离子液体作为溶剂	2~9nm	[32]
液相剥离：阳极电化学辅助剥离	横向尺寸2μm	[33]
液相剥离：添加TAA作为插层剂，阴极电化学辅助剥离	横向尺寸10μm	[34]
黑磷量子点
液相剥离：应用流体力学，高速剪切机辅助剥离	2.25nm	[29]
热溶剂法剥离：NMP作为溶剂，在140℃下溶剂热法处理6h	2.1nm±0.9nm	[37]

复合物	制备方法	光降解效果	光吸收变化	活性物质	参考文献
石墨烯-黑磷烯	化学气相沉积法	光照下降解2-CP，在180min时，30%质量比的石墨烯-黑磷烯分别降87.08%	未提及	·O $2 -$ 和h⁺	[45]
C₆₀-黑磷烯	高能球磨法	50min几乎可以把50mL浓度为0.01mg/mL的RhB降解完全	无变化	·O $2 -$ 和·OH	[46]
Ag-黑磷烯	化学还原法	5%Ag-黑磷烯的反应速率常数为0.574min^-1，高于商用P25	吸收峰变强	未提及	[48]
TiO₂-黑磷烯	溶剂热法	在紫外光照下降解RhB，复合物的反应速率常数为4.62h^-1，黑磷烯仅为0.42h^-1；在可见光照下分别为2.05h^-1和0.23h^-1	未提及	·OH	[53]
黑磷烯-红磷	高能球磨法	30min时降解了89%的RhB，对比对可见光有较好吸收的CdS，其30min降解率仅为32%	无变化	·OH	[55]
黑磷烯-C₃N₄	液相超声法	15min时，10%黑磷烯-C₃N₄降解了98%的RhB，而C₃N₄和黑磷烯分别只有55%和2%	随C₃N₄添加量变化	·O $2 -$	[58]
ATP-黑磷量子点	水热沉积法	在180min的可见光照下，BPA的降解率达到90%	吸收峰变弱	h⁺	[64]
Ag-黑磷烯/GO	还原并沉积	90min后，Ag-黑磷烯/GO和Ag-黑磷烯分别降解了94%和79%的MB	吸收峰变弱	未提及	[65]

复合物	制备方法	光降解效果	光吸收变化	活性物质	参考文献
石墨烯-黑磷烯	化学气相沉积法	光照下降解2-CP，在180min时，30%质量比的石墨烯-黑磷烯分别降87.08%	未提及	·O $2 -$ 和h⁺	[45]
C₆₀-黑磷烯	高能球磨法	50min几乎可以把50mL浓度为0.01mg/mL的RhB降解完全	无变化	·O $2 -$ 和·OH	[46]
Ag-黑磷烯	化学还原法	5%Ag-黑磷烯的反应速率常数为0.574min^-1，高于商用P25	吸收峰变强	未提及	[48]
TiO₂-黑磷烯	溶剂热法	在紫外光照下降解RhB，复合物的反应速率常数为4.62h^-1，黑磷烯仅为0.42h^-1；在可见光照下分别为2.05h^-1和0.23h^-1	未提及	·OH	[53]
黑磷烯-红磷	高能球磨法	30min时降解了89%的RhB，对比对可见光有较好吸收的CdS，其30min降解率仅为32%	无变化	·OH	[55]
黑磷烯-C₃N₄	液相超声法	15min时，10%黑磷烯-C₃N₄降解了98%的RhB，而C₃N₄和黑磷烯分别只有55%和2%	随C₃N₄添加量变化	·O $2 -$	[58]
ATP-黑磷量子点	水热沉积法	在180min的可见光照下，BPA的降解率达到90%	吸收峰变弱	h⁺	[64]
Ag-黑磷烯/GO	还原并沉积	90min后，Ag-黑磷烯/GO和Ag-黑磷烯分别降解了94%和79%的MB	吸收峰变弱	未提及	[65]

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