半導體光觸媒晶面改質工程被認為是調整其物理化學性質並優化材料的光電化學活性的新興策略。在這裡，我們首次報導了BiVO4晶體表面對光電化學甘油氧化反應影響的全方位實驗分析。本研究透過水熱法製備兩種不同晶面暴露面向的單斜晶型BiVO4，分別是晶格生長面向為常規單斜晶型的BiVO4 (R-BVO)，以及控制生長結晶面向為{010}的BiVO4 (C-BVO)，並發現在模擬太陽光的照射下，C-BVO提供了更高的甘油電催化氧化作用。與R-BVO (0.85 mA/cm2)相比，C-BVO記載了更高的光電流密度(1.3 mA/cm2)。除此之外，C-BVO還產生了更高的產量(yield of product)，並且擁有較高的高經濟價值產物二羥基丙酮(DHA)的產物選擇率(selectivity)。實際上，可以發現DHA對C-BVO的產物選擇率大約為60 %，是迄今為止報導的最高值之一。在本研究中發現甘油對於{010}結晶面向的吸附是造成BiVO4催化活性差異的關鍵因素，並且揭曉C-BVO具有更高的電荷載流子密度以及有效的促進電子電洞對分離，導致對甘油氧化和光電流的光電化學活性大大增強。這項研究為晶面結構和催化性能之間的關係提供新見解，這可能為光電化學甘油氧化反應的最佳觸媒設計提供了啟示。

Crystal facet engineering of semiconductor photocatalysts is regarded as an emerging strategy to tune their physicochemical properties and optimize the photoelectrochemical activity of the materials. Herein, we report a comprehensive experimental analysis of the effect of BiVO4 crystal surfaces on the photoelectrochemical glycerol oxidation reaction for the first time. In this study, two types of monoclinic BiVO4 exposed by different crystal facets, i.e. regular monoclinic BiVO4 (R-BVO) and controlled growth crystal facets of {010}-oriented BiVO4 (C-BVO), were prepared by a simple hydrothermal method. It was found that C-BVO delivered a much higher glycerol electrocatalytic oxidation under the simulated sunlight irradiation than R-BVO. Accordingly, a higher photocurrent density of 1.3 mA/cm2 was recorded for C-BVO compared to that of R-BVO (0.85 mA/cm2). Additionally, C-BVO also produced a larger yield of products and slightly higher selectivity toward highly-valuable dihydroxyacetone (DHA) products than its counterpart. Indeed, the selectivity of DHA was found to be about 60% for C-BVO, which is among the highest values reported so far. The preference of glycerol to adsorb on the {010} facet has been found to be a factor that determines the activity of BiVO4. Additionally, it was disclosed that BiVO4 with exposed {010} facets possess higher charge carrier density and efficient intrinsic electron-hole separation, thereby resulting in highly enhanced photoelectrochemical activity toward glycerol oxidation and photocurrent generation. This study provides new insights into the relationship between the facet structure and catalytic properties that may shed light on the design of optimum catalyst toward photoelectrochemical glycerol oxidation reaction.

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