Facet-Engineered Surface and Interface Design of Monoclinic Scheelite Bismuth Vanadate for Enhanced Photocatalytic Performance

Abstract

Monoclinic scheelite bismuth vanadate (mBiVO 4 ) has gradually been in the limelight in recent years because of its great potential in energy conversion and environmental remediation. However, the rapid recombination of photogenerated electron−hole pairs in mBiVO 4 have impeded the improvement of its photocatalytic performance and stability. Therefore, important issues are increasingly focused on finetuning the physicochemical properties of mBiVO 4 at the atomic level based on facetengineered surface and interface design to optimize its selectivity and activity. Herein, the review begins with the fundamental aspects of mBiVO 4 semiconductor, including crystal structure, optical properties, electronic structure, and photocatalytic principles. Then the synthetic methods based on surface and interface design that develop to tailor the facet of mBiVO 4 , along with the discussion of the mechanisms for facet-dependent photocatalytic performance, are presented. Most importantly, the latest advances in facet engineering that have been performed to regulate the surface of single mBiVO 4 and to design the interface structures that are directly involved in the photocatalytic reaction for mBiVO 4based composites are encompassed. Moreover, the photocatalytic application achievements with mBiVO 4 as photocatalysts in energy conversion and environmental remediation are also summarized. Finally, perspectives on the existing challenges and future research directions for this emerging frontier are discussed.

The Thermodynamic Stability, Electronic and Photocatalytic Properties of the ZnWO4(100) Surface as Predicted by Screened Hybrid Density Functional Theory

“… 1 Semiconductor photocatalysis is a process in which the energy generated by electron photoexcitation across semiconductors’ band gaps participates in chemical compounds’ surface reactions. 2 Surface properties such as the area, structure, and composition significantly affect the semiconductor photocatalytic activity. 3 This is because the surface as the reactive species’ adsorption and activation sites significantly impacts the efficiency of surface redox reactions involving photogenerated electrons and holes.…”

Inside‐and‐Out Semiconductor Engineering for CO2 Photoreduction: From Recent Advances to New Trends

“…Herein, exposure of multiple facets in semiconductors to construct a facet junction can propel the electrons or holes to migrate to respective facets, achieving efficient spatial charge separation on the surface. [ 312 ] Meanwhile, it is also desirable that the separated electrons and holes can separately participate in the reduction and oxidation, helpful to the high photocatalytic CO 2 reduction. [ 313–315 ]…”

Photogenerated Charge Separation between Polar Crystal Facets Under a Spontaneous Electric Field

“…The highly reactive polar surfaces usually have high surface energy, [46][47][48][49][50][51][52] and they reduce rapidly during the growth of nanocrystals owing to the minimization of surface energy. [46][47][48][49][50][51][52] It is thus rather challenging to prepare nanocrystals exposed to polar crystal planes.…”

“…The highly reactive polar surfaces usually have high surface energy, [46][47][48][49][50][51][52] and they reduce rapidly during the growth of nanocrystals owing to the minimization of surface energy. [46][47][48][49][50][51][52] It is thus rather challenging to prepare nanocrystals exposed to polar crystal planes. [15][16][17][18][19][23][24][25][26][27][29][30][31][32][33][34][35]37,38,[46][47][48][49][50][51][52] To solve this issue, organic polymers/small molecules or inorganic anions are employed for control of the growth rates of polar crystal planes.…”

“…[46][47][48][49][50][51][52] It is thus rather challenging to prepare nanocrystals exposed to polar crystal planes. [15][16][17][18][19][23][24][25][26][27][29][30][31][32][33][34][35]37,38,[46][47][48][49][50][51][52] To solve this issue, organic polymers/small molecules or inorganic anions are employed for control of the growth rates of polar crystal planes. [15,23,27,[29][30][31]34,38] For example, Cu 2 Se nanowires exposed with {111} crystal planes [34] and ZnO nanodisks exposed with {001} crystal planes [15] have been synthesized by using ethanolglycerol [34] and n-butylamine [15] as the crystal plane controlling agents, respectively.…”