Engineering triple O-Ti-O vacancy associates for efficient water-activation catalysis
Abstract Defect engineering can create various vacancy configurations in catalysts by finely tuning the local electronic and geometric structures of the active sites. However, achieving precise control and identification of these defects remains a significant challenge, and the origin of vacancy con...
Saved in:
| Main Authors: | , , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2025-01-01
|
| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-56190-5 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1832585575599702016 |
|---|---|
| author | Feng Bi Qingjie Meng Yili Zhang Hao Chen Boqiong Jiang Hanfeng Lu Qinghua Liu Hongjun Zhang Zhongbiao Wu Xiaole Weng |
| author_facet | Feng Bi Qingjie Meng Yili Zhang Hao Chen Boqiong Jiang Hanfeng Lu Qinghua Liu Hongjun Zhang Zhongbiao Wu Xiaole Weng |
| author_sort | Feng Bi |
| collection | DOAJ |
| description | Abstract Defect engineering can create various vacancy configurations in catalysts by finely tuning the local electronic and geometric structures of the active sites. However, achieving precise control and identification of these defects remains a significant challenge, and the origin of vacancy configurations in catalysts, especially clustered or associated ones, remains largely unknown. Herein, we successfully achieve the controllable fabrication and quantitative identification of triple O-Ti-O vacancy associate (VOVTiVO) in nanosized Ni-doped TiO2. Experimental and theoretical analyses demonstrate that terminal hydroxyls adsorbed at unsaturated cationic sites play an essential role in boosting VOVTiVO formation, which enhances H2O dissociation and facilitates dissociative OH* deprotonation for defect site regeneration. In contrast, a single VO can be easily saturated by dissociative bridging hydroxyl accumulation, leading to a gradual decrease in the number of active sites. The essential role of VOVTiVO in the Ni-doped TiO2 is evidenced by its comparable catalytic performance in the hydrogen evolution reaction and hydrodechlorination reactions. Our work highlights the importance of engineering vacancy-associated active sites and presents a notable approach for designing highly active and selective catalysts for efficient H2O-involved reactions. |
| format | Article |
| id | doaj-art-7ff3c75829b64fcdb3b0fe076efd6533 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-7ff3c75829b64fcdb3b0fe076efd65332025-01-26T12:41:34ZengNature PortfolioNature Communications2041-17232025-01-0116111110.1038/s41467-025-56190-5Engineering triple O-Ti-O vacancy associates for efficient water-activation catalysisFeng Bi0Qingjie Meng1Yili Zhang2Hao Chen3Boqiong Jiang4Hanfeng Lu5Qinghua Liu6Hongjun Zhang7Zhongbiao Wu8Xiaole Weng9College of Environmental and Resource Sciences, Zhejiang UniversitySchool of Civil & Environmental Engineering and Geography Science, Ningbo UniversityShanghai Academy of Environmental SciencesState Key Laboratory of Particle Detection and Electronics, University of Science and Technology of ChinaSchool of Environmental Science and Engineering, Zhejiang Gongshang UniversityInstitute of Catalytic Reaction Engineering, College of Chemical Engineering, Zhejiang University of TechnologyNational Synchrotron Radiation Laboratory, University of Science and Technology of ChinaState Key Laboratory of Particle Detection and Electronics, University of Science and Technology of ChinaCollege of Environmental and Resource Sciences, Zhejiang UniversityCollege of Environmental and Resource Sciences, Zhejiang UniversityAbstract Defect engineering can create various vacancy configurations in catalysts by finely tuning the local electronic and geometric structures of the active sites. However, achieving precise control and identification of these defects remains a significant challenge, and the origin of vacancy configurations in catalysts, especially clustered or associated ones, remains largely unknown. Herein, we successfully achieve the controllable fabrication and quantitative identification of triple O-Ti-O vacancy associate (VOVTiVO) in nanosized Ni-doped TiO2. Experimental and theoretical analyses demonstrate that terminal hydroxyls adsorbed at unsaturated cationic sites play an essential role in boosting VOVTiVO formation, which enhances H2O dissociation and facilitates dissociative OH* deprotonation for defect site regeneration. In contrast, a single VO can be easily saturated by dissociative bridging hydroxyl accumulation, leading to a gradual decrease in the number of active sites. The essential role of VOVTiVO in the Ni-doped TiO2 is evidenced by its comparable catalytic performance in the hydrogen evolution reaction and hydrodechlorination reactions. Our work highlights the importance of engineering vacancy-associated active sites and presents a notable approach for designing highly active and selective catalysts for efficient H2O-involved reactions.https://doi.org/10.1038/s41467-025-56190-5 |
| spellingShingle | Feng Bi Qingjie Meng Yili Zhang Hao Chen Boqiong Jiang Hanfeng Lu Qinghua Liu Hongjun Zhang Zhongbiao Wu Xiaole Weng Engineering triple O-Ti-O vacancy associates for efficient water-activation catalysis Nature Communications |
| title | Engineering triple O-Ti-O vacancy associates for efficient water-activation catalysis |
| title_full | Engineering triple O-Ti-O vacancy associates for efficient water-activation catalysis |
| title_fullStr | Engineering triple O-Ti-O vacancy associates for efficient water-activation catalysis |
| title_full_unstemmed | Engineering triple O-Ti-O vacancy associates for efficient water-activation catalysis |
| title_short | Engineering triple O-Ti-O vacancy associates for efficient water-activation catalysis |
| title_sort | engineering triple o ti o vacancy associates for efficient water activation catalysis |
| url | https://doi.org/10.1038/s41467-025-56190-5 |
| work_keys_str_mv | AT fengbi engineeringtripleotiovacancyassociatesforefficientwateractivationcatalysis AT qingjiemeng engineeringtripleotiovacancyassociatesforefficientwateractivationcatalysis AT yilizhang engineeringtripleotiovacancyassociatesforefficientwateractivationcatalysis AT haochen engineeringtripleotiovacancyassociatesforefficientwateractivationcatalysis AT boqiongjiang engineeringtripleotiovacancyassociatesforefficientwateractivationcatalysis AT hanfenglu engineeringtripleotiovacancyassociatesforefficientwateractivationcatalysis AT qinghualiu engineeringtripleotiovacancyassociatesforefficientwateractivationcatalysis AT hongjunzhang engineeringtripleotiovacancyassociatesforefficientwateractivationcatalysis AT zhongbiaowu engineeringtripleotiovacancyassociatesforefficientwateractivationcatalysis AT xiaoleweng engineeringtripleotiovacancyassociatesforefficientwateractivationcatalysis |