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Bi2O3/BiVO4@graphene oxide van der Waals heterostructures with enhanced photocatalytic activity toward oxygen generation

https://doi.org/10.1016/j.jcis.2021.02.079Get rights and content

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  • A multi-dimensional (2D/3D) Bi2O3/BiVO4@GO is designed by self-assembly strategy;

  • Bi2O3/BiVO4@GO heterojunction is self-assembled by van der Waals interactions;

  • The vdW heterostructure exhibits superior O2 evolution of 1828 µmol h−1 g−1.

  • The strategy paves new avenue to fabricate multi-dimensional vdW heterostructures.

Abstract

The van der Waals (vdW) integration enables to create heterostructures with intimate contact and bring new opportunities. However, it is not confined to layered materials but can also be generally extended to 3D materials. Multidimensional Bi2O3/BiVO4@graphene oxide (GO) van der Waals heterostructures are synthesized by one-pot wet chemistry method. Bi2O3/BiVO4 composite nanoparticles are self-assembled with GO framework by vdW interaction to form vdW heterostructures, in which GO framework allows short electron transport distance and rapid charge transfer and provides massive reactive sites. Such self-assembled heterostructures show a superior high photoactivity towards oxygen evolution with an enhanced oxygen generation rate of 1828 µmol h−1 g−1, nearly 3 times than that of pure BiVO4, attributed to the accelerated charge separation and transfer processes of Bi2O3/BiVO4@GO vdW heterostructures. This study indicates that our strategy provides a new avenue towards fabricating multi-dimensional vdW heterostructures and inspiring more innovative insights in oxygen evolution field.

Introduction

Two-dimensional (2D) materials, including MoS2 [1], graphite [2], WS2 [3], MoSe2 [4], have attracted worldwide attentions in the application in energy storage and conversion. Particularly, 2D graphene oxide (GO) has high specific surface, high strength, high stability, and high carrier mobility and shows great potentials in photocatalytic, thermal, and electrical fields [5]. Meanwhile, oxygen-rich functional groups of GO provide abundant reactive sites, which can enhance the interaction between their photocatalytic hybrid materials to facilitate electron transfer to enhance photocatalytic efficiency [6].

Currently, several universal strategies are used to assemble different 2D building blocks to form heterostructures by using physical or chemical interactions [7], [8]. Strong covalent bonds provide in-plane stability, whereas relatively weak, van-der-Waals-like forces are sufficient to keep the stack together. Therefore, these different 2D crystals can be stacked each another by using weak van der Waals (vdW) forces [9]. In fact, a few layered materials, such as Bi2Te3/FeTe [10], MoS2/Au [11] and InSe/graphene heterostructures [12], [13] have been reported to link together by vdW forces for designing heterostructures. Atomic interfaces between layered materials accelerate the vdW interaction. Therefore, the vdW integration enables to create a great deal of heterostructures with intimate contact and bring new opportunities. Multilayer graphene vdW heterostructures were constructed using hexagonal boron nitride (h-BN) as a substrate [14], [15]. Similarly, graphene/MoS2 [16] and BN/graphene/BN [17] were synthesized to improve charge mobility of graphene with the construction of 2D/2D vdW integration. Such vdW integration can promote the separation of interfacial carriers and enable access to fast charge speed.

Actually, vdW interactions are not confined to interactions in layered materials and can also be generally extended to 3D materials [18]. Various multi-dimensional (2D/3D) heterostructures with multi-functionalities can be elaborately designed by using the different rational hybridization methods of different dimensional materials [19], [20], [21]. Their properties have been significantly enhanced by compensating individual weakness. Recently, a 2D/3D vdW heterostructure consisting of 2D triazine-based framework and 3D triazine-based graphdiyene has been reported for hydrogen evolution reaction [22]. A 3D/2D/2D structured BiVO4/FeVO4@rGO has been reported to have an enhanced transport and separation efficiency of photogenerated carriers [23]. Likewise, 2D/3D/2D rGO/Fe2O3/g-C3N4 nanocomposites were designed to inhibit the recombination rate of photoexcited charge carriers [24]. These fabricated multi-dimensional architectures, assembled with micrometer- and nanometer-scaled building blocks, exhibit unique photocatalytic activity compared to the individual structures [25], [26]. Therefore, such an approach provides various material choices and selectable properties and can be applicable for developing 3D systems.

In this work, we report a facile self-assembly of a multi-dimensional (2D/3D) Bi2O3/BiVO4@GO vdW heterostructures via one-pot “wet” chemistry approach. The synthesized Bi2O3/BiVO4 particle with a small diameter shows short electron transport distance. By stacking GO framework on Bi2O3/BiVO4, 2D/3D heterostructures is formed and inherits the excellent properties of GO framework, including high specific surface area and high carrier mobility. Such 2D/3D vdW heterostructures process massive reactive sites and accelerated electron transfer, thus have significantly enhanced photocatalytic activity toward oxygen generation.

Section snippets

Synthesis of 2D/3D Bi2O3/BiVO4@GO vdW heterostructures

All chemicals were obtained and used from commercial sources as analytical pure reagents without further purification. The 2D/3D Bi2O3/BiVO4@GO vdW heterostructures were self-assembled by one-pot “wet” chemistry approach. 0.4 mmol Bi(NO3)3·5H2O (Sinopharm Chemical Reagent Co., Ltd., 99%) was firstly dissolved in 16 mL of glycerol after stirring for 1 h (h). Then, 0.4 mmol NaVO3·2H2O (Sinopharm Chemical Reagent Co., Ltd., 99%) was dissolved in another 16 mL of deionized water. It can be clearly

Characterization of photocatalyst

Fig. 1 shows the typical X-ray diffractometry (XRD) patterns of as-prepared pure BiVO4 and 2D/3D Bi2O3/BiVO4@GO heterostructures. As can be seen, all the products have monoclinic BiVO4. The intensive (2 2 1) peak (inset of Fig. 1) shows that the Bi2O3/BiVO4@GO heterostructures have Bi2O3 phase, indicating coexistence of Bi2O3 and BiVO4 in the heterostructure photocatalysts. According to the results of whole pattern fitting and Rietveld refinement, the molar ratio of Bi2O3 and BiVO4 is 4:96. In

Conclusion

In conclusion, we use a facile self-assembly technique to fabricate 2D/3D Bi2O3/BiVO4@GO vdW heterostructures, which exhibits an enhanced O2 evolution rate of 1828 µmol h−1 g−1, nearly 3 times than that of pure BiVO4. The enhanced photocatalytic activity may originate from the 2D/3D heterojunction with van der Waals interactions. The heterostructures composed of 2D GO and 3D Bi2O3/BiVO4 is expected to play a significant role in promoting electron transfer and providing massive reactive sites.

CRediT authorship contribution statement

Yaxin Bi: Investigation, Data curation, Writing - original draft. Yanling Yang: Conceptualization, Methodology, Writing - review & editing. Xiao-Lei Shi: Investigation, Writing - review & editing. Lei Feng: Investigation. Xiaojiang Hou: Investigation. Xiaohui Ye: Investigation. Li Zhang: Investigation. Guoquan Suo: Investigation. Jingeng Chen: Investigation. Zhi-Gang Chen: Conceptualization, Methodology, Visualization, Writing - review & editing.

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.

Acknowledgments

The authors acknowledge financial support from the National Natural Science Foundation of China (Grant Nos.: 51464020, 51101076, 51704188, 51802181, 61705125 and 51702199), and Australian Research Council.

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