Huang Haowei, Zhao Jiwu, Weng Bo, Lai Feili, Zhang Menglong, Hofkens Johan, Roeffaers Maarten B J, Steele Julian A, Long Jinlin
cMACS, Department of Microbial and Molecular Systems KU Leuven, Celestijnenlaan 200F, 3001, Leuven, Belgium.
State Key Lab of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, 350116, P. R. China.
Angew Chem Int Ed Engl. 2022 Jul 11;61(28):e202204563. doi: 10.1002/anie.202204563. Epub 2022 May 19.
We demonstrate a new case of materials-gene engineering to precisely design photocatalysts with the prescribed properties. Based on theoretical calculations, a phase-doping strategy was proposed to regulate the pathways of CO conversion over Au nanoparticles (NPs) loaded TiO photocatalysts. As a result, the thermodynamic bottleneck of CO -to-CO conversion is successfully unlocked by the incorporation of stable twinning crystal planes into face-centered cubic (fcc) phase Au NPs. Compared to bare pristine TiO , the activity results showed that the loading of regular fcc-Au NPs raised the CO production by 18-fold but suppressed the selectivity from 84 % to 75 %, whereas Au NPs with twinning (110) and (100) facets boosted the activity by nearly 40-fold and established near unity CO selectivity. This enhancement is shown to originate from a beneficial shift in the surface reactive site energetics arising at the twinned stacking fault, whereby both the CO reaction energy and desorption energy were significantly reduced.
我们展示了一个材料基因工程的新案例，用于精确设计具有规定性能的光催化剂。基于理论计算，提出了一种相掺杂策略来调控负载在TiO光催化剂上的金纳米颗粒（NPs）上CO转化的路径。结果，通过将稳定的孪晶面引入面心立方（fcc）相金纳米颗粒中，成功消除了CO到CO转化的热力学瓶颈。与裸露的原始TiO相比，活性结果表明，负载规则的fcc-Au NPs使CO产量提高了18倍，但选择性从84%降至75%，而具有孪晶（110）和（100）面的金纳米颗粒使活性提高了近40倍，并实现了接近100%的CO选择性。这种增强被证明源于孪晶堆垛层错处表面反应位点能量的有利变化，由此CO反应能量和解吸能量都显著降低。
