A review on black-phosphorus-based composite heterojunction photocatalysts for energy and environmental applications

https://doi.org/10.1016/j.seppur.2022.122833Get rights and content

Highlights

  • Basic properties and common preparation methods of BP are introduced.

  • Categories of BP-based heterojunction photocatalysts are summarized.

  • Photocatalytic applications in energy and environment are discussed.

  • Challenges and perspectives facing BP-based heterojunctions are proposed.

Abstract

In the past decades, using semiconductor-based photocatalytic technology to accomplish solar-to-chemical energy conversion has been a potential strategy for simultaneously mitigating the severe environmental and energy crises. Black phosphorus (BP) is a promising nonmetal photocatalyst with numerous advantages, such as an adjustable direct band gap, a wide light absorption range, and ultrahigh charge carrier mobility. However, pure BP photocatalysts exhibit unsatisfactory performance because of poor ambient stability and fast recombination of the photogenerated electrons and holes. To overcome these obstacles, much research has focused on constructing BP-based heterojunction photocatalysts by combining BP with other catalytic materials. In this review, a brief introduction of the crystal structure, optical absorption, and electrical properties of BP photocatalysts is firstly presented. Then, the common preparation methods of BP with different dimensions are addressed. In accordance with the separation and migration path of the photogenerated electron-hole pairs at the interface, BP-based heterojunction photocatalysts are classified into Type I, Type II, Z-scheme, and S-scheme heterojunctions. In addition, three modification strategies for synergistically enhancing the ambient stability and catalytic performance of BP-based heterojunctions are presented, including modification with metal nanoparticles, in situ growth of metal phosphides, and combination with carbon-based materials. Thereafter, a series of applications in energy and environmental fields is illustrated. Finally, some personal perspectives are given on future directions for developing BP-based heterojunction photocatalysts.

Introduction

Currently, with the continuous advancement of global industrialization, traditional fossil energy such as petroleum, coal, and natural gas are excessively consumed [1], [2]; a large quantity of harmful waste is simultaneously generated and discharged into the environment, on which humans depend [3], [4]. Therefore, foreseeable energy shortages and substantial environmental pollution are two important topics on a global level. As a promising strategy to manage energy and environment concerns, semiconductor-based photocatalytic technology has received extensive interest worldwide because of its low cost, high efficiency, and absence of secondary pollution [5], [6], [7]. For one thing, this technology can convert inexhaustible and clean solar energy into valuable and storable chemical energy through photocatalytic overall water splitting [8], [9], [10], carbon dioxide (CO2) reduction [11], [12], and nitrogen (N2) fixation [13]. For another, one can also utilize this technology to directly use solar energy, and in so doing drive semiconductor materials to produce various active species for removing various harmful and toxic contaminants [14], [15], [16].

Many valuable semiconductor photocatalysts have been discovered with the accelerated development of the photocatalysis field in recent decades, including metal oxides [17], [18], metal sulfides [19], [20], graphitic carbon nitride (g-C3N4) [21], [22], [23], Bi-based materials [24], [25], [26], perovskite [27], and metal–organic frameworks [28], [29], [30]. Recently, black phosphorus (BP) has been widely investigated and applied to energy- and environment-related photocatalytic fields because of its unique intrinsic properties [31], [32], [33], [34]. Specifically, one can readily peel off bulk BP into zero-dimensional (0D) quantum dot (QD) and two-dimensional (2D) nanosheets (NSs) structures due to bulk BP’s weak van der Waals interlayer interactions [35], [36]. Meanwhile, BP possesses a direct tunable band gap from 0.3 eV for bulk BP to 2.0 eV for monolayer BP [37], and endows strong responses in both the visible and near-infrared region. Furthermore, the excellent electrical conductivity and ultrahigh charge carrier mobility of BP further indicates its suitability for photocatalysis [38], [39].

However, the photocatalytic efficiency of pure BP materials is unsatisfactory, mainly owing to the fast rate of recombination of the photogenerated carriers and poor chemical stability upon exposure to light, oxygen, and water in photocatalytic reactions [40], [41], [42], [43]. Up to present, a stable internal electric field forms between BP and other semiconductor catalysts by construction of suitable heterojunctions, which can enable spatial separation and transfer of the photogenerated electron-hole pairs [44], [45], [46]. In addition, building heterojunctions that exhibit strong chemical bonding is a means of improving the stability of BP photocatalysts [47], [48]. Although much research has been designed and reported on BP-based composite heterojunction photocatalysts in recent years, there are few comprehensive reviews that summarize the types of BP-based heterojunction materials and their applications in the fields of energy conversion and environmental remediation.

In this review, first, the basic properties of BP photocatalysts are concisely introduced; these properties include the crystal and band structure, optical absorption, and electrical properties. Second, the common preparation methods of BP with different dimensional structures (bulk BP, 2D BP NSs, and 0D BP QDs) are addressed. The third section focuses on discussing the classifications of BP-based heterojunction systems, which can be mainly divided into Type I, Type II, Z-scheme, and S-scheme heterojunctions (Fig. 1). Importantly, three modification strategies for synergistically enhancing the ambient stability and catalytic performance of BP materials are presented, including modification with metal nanoparticles, in situ growth of metal phosphides, and combination with carbon-based materials. Thereafter, the energy and environmental applications of BP-based composite heterojunction photocatalysts BP-based heterojunction photocatalysts are enumerated. Finally, some personal viewpoints are put forward regarding the current challenges and further research directions of BP-based heterojunction composite photocatalysts.

Section snippets

Crystal and band structure of BP

BP, as one of the important members of the P family, has the advantages of nontoxicity and higher thermodynamic stability at ambient temperatures in comparison with white phosphorus (WP) and red phosphorus (RP). Fig. 2a and b show the typical crystal structure of BP [49]; In the monolayer BP, each P atom is covalently linked with three adjacent P atoms in the form of Psingle bondP σ bonds. These monolayer BP with the interlayer spacing of about 5.5 Å are stacked together to form bulk BP through van der

Fabrication methods and morphological structures of BP

Based on the dimensional structure, BP species can be classified into three types: bulk BP, 2D BP NSs, and 0D BP QDs. In the following section, fabrication methods and the morphological structures of BP are briefly introduced.

Categories of BP-based heterojunction photocatalysts

In general, design and construction of heterojunction photocatalysts consisted of different semiconductors is an effective strategy for obtaining high performance in photocatalytic reactions. In recent years, a variety of BP-based heterojunction photocatalysts have been developed and fabricated due to the following three main advantages. First, building a heterojunction interface between BP and other photocatalysts can achieve efficient spatial separation and transfer of the photogenerated

Approaches for improving the stability of BP photocatalysts

In the photocatalytic process, pure BP catalyst displays poor chemical stability and tends to readily oxidize upon exposure to light, oxygen, and water because the P atoms in BP have the lone pair of electrons that are good chemical adsorption active sites for oxygen molecules [129], [130]. The general oxidative degradation mechanism of BP is briefly expressed as follows (Fig. 14) [131]: the oxygen molecules on the BP surface first react with the photogenerated electrons and produce superoxide

Photocatalytic application of BP-based heterojunction photocatalysts

Semiconductor photocatalytic technology has enormous potential for helping to solve environment and energy issues, because this technology has an active role in achieving solar-to-chemical energy conversion. In recent years, lots of BP-based heterojunction photocatalysts have been developed and applied to photocatalytic CO2 conversion, nitrogen fixation, and water splitting, as well as remediation of water/air pollution.

Conclusions and perspectives

In recent years, BP with various dimensional structures has been one of the most promising nonmetallic semiconductor photocatalytic materials owing to its distinctive optical and electrical properties. However, insufficient ambient stability and rapid recombination of the photogenerated carriers for pure BP seriously weaken its photocatalytic performance. Construction of a heterojunction interface between BP and other catalysts can effectively suppress surface electron-hole recombination. Thus,

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

We gratefully acknowledge the financial support provided by the National Key R&D Program of China (2020YFC1808401), National Natural Science Foundation of China (22078213, 21938006, 51973148, 21776190), cutting-edge technology basic research project of Jiangsu (BK20202012) and the project supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions, China (PAPD). Guping Zhang is also grateful for support from the Project funded by China Postdoctoral Science

Guping Zhang received his PhD from Soochow University (Suzhou, China) in 2021. He is currently a postdoctoral researcher under the supervision of Prof. Jianmei Lu and Dongyun Chen at College of Chemistry, Chemical Engineering and Materials Science in Soochow University. His research interests focus on design and fabrication of micro-nano composite materials for adsorption and photocatalytic application.

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    Guping Zhang received his PhD from Soochow University (Suzhou, China) in 2021. He is currently a postdoctoral researcher under the supervision of Prof. Jianmei Lu and Dongyun Chen at College of Chemistry, Chemical Engineering and Materials Science in Soochow University. His research interests focus on design and fabrication of micro-nano composite materials for adsorption and photocatalytic application.

    Dongyun Chen is a professor in the College of Chemistry, Chemical Engineering and Materials Science, Soochow University. He received his B.S. and Ph.D. degree at the College of Chemistry, Chemical Engineering and Materials Science, Soochow University in 2007 and 2012, respectively. His current research interests are focused on design and fabrication of novel photo/electro-catalysts for energy conversion and pollutant degradation.

    Jianmei Lu is a professor of the College of Chemistry, Chemical Engineering and Materials Science, Soochow University and a fellow of the Chemical Industry and Engineering Society of China. She received her Ph.D. degree in polymer chemistry from Zhejiang University in 1999 and appointed as professor of Soochow University in 2000. Her current research interests involve organic and polymer electronic memory functional materials, functional materials with adsorption and catalytic properties for environmental remediation and industrial application.

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