Insight into mechanism for remarkable photocatalytic hydrogen evolution of Cu/Pr dual atom co-modified TiO2

被引:0
作者
Zheng, Hongshun [1 ,2 ]
Zi, Baoye [1 ]
Zhou, Tong [1 ]
Qiu, Guoyang [1 ]
Luo, Zhongge [1 ]
Lu, Qingjie [1 ]
Santiago, Alain Rafael Puente [3 ,4 ]
Zhang, Yumin [1 ]
Zhao, Jianhong [1 ]
Zhang, Jin [1 ]
He, Tianwei [1 ]
Liu, Qingju [1 ,2 ]
机构
[1] Yunnan Univ, Natl Ctr Int Res Photoelect & Energy Mat, Sch Mat Sci & Engn, Yunnan Key Lab Micro Nano Mat & Technol, Kunming 650091, Peoples R China
[2] Southwest United Grad Sch, Kunming 650091, Peoples R China
[3] Univ Texas Austin, Walker Dept Mech Engn, Austin, TX 78712 USA
[4] Florida Int Univ FIU, Dept Chem & Biochem, Miami, FL USA
基金
中国国家自然科学基金;
关键词
INITIO MOLECULAR-DYNAMICS; TOTAL-ENERGY CALCULATIONS; H-2; PRODUCTION; UP-CONVERSION; WATER; TRANSITION; METAL; EFFICIENCY; METHANOL;
D O I
10.1039/d4nh00196f
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The development of high-activity photocatalysts is crucial for the current large-scale development of photocatalytic hydrogen applications. Herein, we have developed a strategy to significantly enhance the hydrogen photocatalytic activity of Cu/Pr di-atom co-modified TiO2 architectures by selectively anchoring Cu single atoms on the oxygen vacancies of the TiO2 surface and replacing a trace of Ti atoms in the bulk with rare earth Pr atoms. Calculation results demonstrated that the synergistic effect between Cu single atoms and Pr atoms regulates the electronic structure of Cu/Pr-TiO2, thus promoting the separation of photogenerated carriers and their directional migration to Cu single atoms for the photocatalytic reaction. Furthermore, the d-band center of Cu/Pr-TiO2, which is located at -4.70 eV, optimizes the adsorption and desorption behavior of H*. Compared to TiO2, Pr-TiO2, and Cu/TiO2, Cu/Pr-TiO2 displays the best H* adsorption Gibbs free energy (-0.047 eV). Furthermore, experimental results confirmed that the photogenerated carrier lifetime of Cu/Pr-TiO2 is not only the longest (2.45 ns), but its hydrogen production rate (34.90 mmol g(-1) h(-1)) also significantly surpasses those of Cu/TiO2 (13.39 mmol g(-1) h(-1)) and Pr-TiO2 (0.89 mmol g(-1) h(-1)). These findings open up a novel atomic perspective for the development of optimal hydrogen activity in dual-atom-modified TiO2 photocatalysts.
引用
收藏
页码:1532 / 1542
页数:11
相关论文
共 57 条
[1]   Review of one-dimensional and two-dimensional nanostructured materials for hydrogen generation [J].
Babu, Veluru Jagadeesh ;
Vempati, Sesha ;
Uyar, Tamer ;
Ramakrishna, Seeram .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2015, 17 (05) :2960-2986
[2]   Recent advances in making nano-sized TiO2 visible-light active through rare-earth metal doping [J].
Bingham, Sonny ;
Daoud, Walid A. .
JOURNAL OF MATERIALS CHEMISTRY, 2011, 21 (07) :2041-2050
[3]   IMPROVED TETRAHEDRON METHOD FOR BRILLOUIN-ZONE INTEGRATIONS [J].
BLOCHL, PE ;
JEPSEN, O ;
ANDERSEN, OK .
PHYSICAL REVIEW B, 1994, 49 (23) :16223-16233
[4]   Lanthanide Luminescence for Biomedical Analyses and Imaging [J].
Buenzli, Jean-Claude G. .
CHEMICAL REVIEWS, 2010, 110 (05) :2729-2755
[5]   Multi-stepwise charge transfer via MOF@MOF/TiO2 dual-heterojunction photocatalysts towards hydrogen evolution [J].
Chen, Yao ;
Yang, Dong ;
Xin, Xin ;
Yang, Zhongshan ;
Gao, Yuchen ;
Shi, Yonghui ;
Zhao, Zhanfeng ;
An, Ke ;
Wang, Wenjing ;
Tan, Jiangdan ;
Jiang, Zhongyi .
JOURNAL OF MATERIALS CHEMISTRY A, 2022, 10 (17) :9717-9725
[6]   Water Splitting with a Single-Atom Cu/TiO2 Photocatalyst: Atomistic Origin of High Efficiency and Proposed Enhancement by Spin Selection [J].
Cheng, Cheng ;
Fang, Wei-Hai ;
Long, Run ;
Prezhdo, Oleg, V .
JACS AU, 2021, 1 (05) :550-559
[7]   Influence of Pr3+ doping on the synthesis of colloidal sols and nanoparticulate TiO2 xerogels and their photocatalytic activity [J].
Colomer, Maria T. ;
Duarte, Karent J. ;
Ortiz, Angel L. ;
Fabio Mercado, D. ;
Ballesteros-Rueda, Luz M. .
MATERIALS CHARACTERIZATION, 2021, 182
[8]   The sustainability of green hydrogen: An uncertain proposition [J].
Cremonese, L. ;
Mbungu, G. K. ;
Quitzow, R. .
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, 2023, 48 (51) :19422-19436
[9]   Correlation between Electronic Configuration and Magnetic Stability in Dysprosium Single Atom Magnets [J].
Donati, Fabio ;
Pivetta, Marina ;
Wolf, Christoph ;
Singha, Aparajita ;
Waeckerlin, Christian ;
Baltic, Romana ;
Fernandes, Edgar ;
De Groot, Jean-Guillaume ;
Ahmed, Safa Lamia ;
Persichetti, Luca ;
Nistor, Corneliu ;
Dreiser, Jan ;
Barla, Alessandro ;
Gambardella, Pietro ;
Brune, Harald ;
Rusponi, Stefano .
NANO LETTERS, 2021, 21 (19) :8266-8273
[10]   ELECTROCHEMICAL PHOTOLYSIS OF WATER AT A SEMICONDUCTOR ELECTRODE [J].
FUJISHIMA, A ;
HONDA, K .
NATURE, 1972, 238 (5358) :37-+