甘露醇与酸碱度协同调控氧空位修饰钼酸铋纳米棒的合成及其高效光催化固氮活性  

Mannitol and acidity co-tuned synthesis of oxygen-vacancy-modified bismuth molybdate nanorods for efficient photocatalytic nitrogen reduction to ammonia

作　　者：王国安 邓全花 李海平 侯万国 Guoan Wang;Quanhua Deng;Haiping Li;Wanguo Hou(National Engineering Research Center for Colloidal Materials,School of Chemistry and Chemical Engineering,Shandong University,Jinan 250100,China;Stanley fertilizer(plain)Co.,Ltd,Dezhou 250100,China)

机构地区：[1]National Engineering Research Center for Colloidal Materials,School of Chemistry and Chemical Engineering,Shandong University,Jinan 250100,China [2]Stanley fertilizer(plain)Co.,Ltd,Dezhou 250100,China

出　　处：《Science China Materials》2023年第4期1435-1446,共12页中国科学（材料科学（英文版）

基　　金：supported by the National Natural Science Foundation of China(21872082);the Young Scholars Program of Shandong University in China(2018WLJH39)。

摘　　要：半导体中氧空位(Ov)能够吸附和活化N_(2)分子,是光催化N_(2)还原反应(NRR)的活性位点,但仍亟待开发简单、有效的形成Ov的方法.本文通过甘露醇存在下的水热过程,在Bi_(2)MoO_(6)纳米短棒(BMO SNR)中的Mo位点上选择性形成Ov,且样品的Ov含量、SNR长度与直径以及比表面积均可通过pH进行有效调控.含Ov最多的BMO SNR呈现最强的可见光吸收、光生电荷分离和光催化NRR性能,其纯水中NRR速率约为无甘露醇存在下合成的BMO纳米片的107倍,420 nm表观量子产率达到了2.78%,优于所有报道的BMO基光催化剂.本文提出了一种新颖、简单的方法对BMO进行形貌调控,且选择性形成Ov,从而增进其光催化NRR活性.Oxygen vacancies(Ovs)in semiconductors,which can adsorb and activate N_(2)molecules,are active sites for photocatalytic nitrogen reduction to ammonia.However,simple and effective methods for creating Ovs still need to be explored.Herein,mannitol was used to selectively create Ovs at Mo in Bi_(2)MoO_(6)(BMO)and form BMO short nanorods(SNRs)through a hydrothermal process,with the Ov content,SNR size,and surface area of the sample effectively tuned by pH.BMO SNRs containing the most Ovs exhibit the highest visible light absorption,fastest photoexcited charge separation,and best photocatalytic nitrogen fixation performance,with an N_(2)reduction reaction rate in pure water reaching approximately 107-fold that of BMO nanosheets synthesized in the absence of mannitol,and an apparent quantum yield of 2.78%at 420 nm,superior to all of the reported BMO-based photocatalysts.This work provides a new and simple method for selective Ov creation and the morphological tuning of BMO to expedite the photocatalytic N_(2)reduction.

关 键 词：光生电荷分离 形貌调控 BMO 还原反应 光催化 氧空位 甘露醇 协同调控 

分 类 号：TQ113.26[化学工程—无机化工] TQ426