Charge carrier transport dynamics in W/Mo-doped BiVO4: first principles-based mesoscale characterization
文献类型：期刊论文
| 作者 | Dupuis, Michel1,3,4; Pasumarthi, Viswanath1; Liu, Taifeng2; Li, Can4,5 |
| 刊名 | JOURNAL OF MATERIALS CHEMISTRY A
 |
| 出版日期 | 2019-02-21 |
| 卷号 | 7期号:7页码:3054-3065 |
| ISSN号 | 2050-7488 |
| DOI | 10.1039/c8ta09899a |
| 通讯作者 | Liu, Taifeng(tfliu@vip.henu.edu.cn) ; Dupuis, Michel(mdupuis2@buffalo.edu) |
| 英文摘要 | We present mesoscale characterization of carrier transport in W/Mo-doped ms-BiVO4 (BVO) to supplement our earlier study of electron and hole transport in bulk BVO. The mesoscale kinetic Monte Carlo (KMC) approach, supported by first principles-determined electron and hole hopping rates, captures the complex dynamics of electron carriers arising from light absorption and from metal doping. The computations and simulations support the observation that, for the doping level used in experiment, doping atoms do not affect significantly the transport dynamics of the charge carriers compared to stoichiometric BVO. W/Mo doping increases the electron carrier concentration and consequently the electrode conductivity. We used a density functional theory DFT + U method to characterize the electronic structure of doped BVO. Each W and Mo atom brings one more valence electron than a V atom. These excess electrons are mobile. We adopted the theories and methods of our earlier investigations on BVO. The DFT + U theory affords an accurate description of small electron polarons with electrons localized on W or Mo or V, as well as of the hopping barriers from W/Mo-to-V or V-to-V. Calculations on a 3 x 3 x 1 supercell of W/Mo-doped ms-BVO indicate that the excess electron from W or Mo does not reside on the doping atom. There is a shallow interaction region around the doping atom where the excess electron localized on a V atom is more stable than when localized on the doping atom and slightly more stable than when the excess electron is localized far away from the doping atom. This region is two nearest V atom-wide for W and three nearest atom-wide for Mo. The depths of these stabilization regions are very small, similar to-0.65 k(B)T (at 300 K) for W and similar to-0.73 k(B)T for Mo. Calculated V-to-V hopping barriers in the doped material are little affected within the region and not affected outside the region. Using our recently developed lattice-based kinetic Monte Carlo code adapted to account for doping atoms and their energy stabilization regions, we calculated the diffusivity of electrons for carrier density relevant to experiment as well as the conductivity. The stabilization regions have little effect on the diffusivity compared to the stoichiometric system because of the smallness of the stabilization. The diffusivity is found to decrease slightly with an increasing number of carriers, but the conductivity of a system with electron polarons arising from doping together with light absorption increases compared to that of the un-doped system. This work will set the foundation to study electron transport in gradient (W/Mo)-doped systems and other mixed phase systems. |
| WOS关键词 | KINETIC MONTE-CARLO ; SCANNING ELECTROCHEMICAL MICROSCOPY ; TOTAL-ENERGY CALCULATIONS ; SMALL-POLARON ; ADIABATIC THEORY ; OXIDE ; PHOTOANODES ; CATALYSTS ; MOBILITY ; MO |
| 资助项目 | National Natural Science Foundation of China[21703054] ; University at Buffalo ; U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences[DE-SC0019086] |
| WOS研究方向 | Chemistry ; Energy & Fuels ; Materials Science |
| 语种 | 英语 |
| WOS记录号 | WOS:000458682100053 |
| 出版者 | ROYAL SOC CHEMISTRY |
| 资助机构 | National Natural Science Foundation of China ; National Natural Science Foundation of China ; University at Buffalo ; University at Buffalo ; U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences ; U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; University at Buffalo ; University at Buffalo ; U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences ; U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; University at Buffalo ; University at Buffalo ; U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences ; U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; University at Buffalo ; University at Buffalo ; U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences ; U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences |
| 源URL | [http://cas-ir.dicp.ac.cn/handle/321008/166046]  |
| 专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
| 通讯作者 | Dupuis, Michel; Liu, Taifeng |
| 作者单位 | 1.SUNY Buffalo, Dept Chem & Biol Engn, Buffalo, NY 14260 USA 2.Henan Univ, Collaborat Innovat Ctr Nano Funct Mat & Applicat, Natl & Local Joint Engn Res Ctr Appl Technol Hybr, Kaifeng 475004, Peoples R China 3.SUNY Buffalo, Computat & Data Enabled Sci & Engn Program, Buffalo, NY 14260 USA 4.Dalian Inst Chem Phys, Dalian Natl Lab Clean Energy, Dalian, Peoples R China 5.Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian, Peoples R China |
| 推荐引用方式 GB/T 7714 | Dupuis, Michel,Pasumarthi, Viswanath,Liu, Taifeng,et al. Charge carrier transport dynamics in W/Mo-doped BiVO4: first principles-based mesoscale characterization[J]. JOURNAL OF MATERIALS CHEMISTRY A,2019,7(7):3054-3065. |
| APA | Dupuis, Michel,Pasumarthi, Viswanath,Liu, Taifeng,&Li, Can.(2019).Charge carrier transport dynamics in W/Mo-doped BiVO4: first principles-based mesoscale characterization.JOURNAL OF MATERIALS CHEMISTRY A,7(7),3054-3065. |
| MLA | Dupuis, Michel,et al."Charge carrier transport dynamics in W/Mo-doped BiVO4: first principles-based mesoscale characterization".JOURNAL OF MATERIALS CHEMISTRY A 7.7(2019):3054-3065. |
入库方式： OAI收割
来源：大连化学物理研究所
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