Exploring Burstein–Moss type effects in nickel doped hematite dendrite nanostructures for enhanced photo-electrochemical water splitting

文献信息

发布日期 2019-08-06
DOI 10.1039/C9CP04132J
影响因子 3.676
作者

Soniya Gahlawat, Jaspreet Singh, Ashok Kumar Yadav, Pravin P. Ingole


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摘要

The Burstein–Moss (B–M) effect, which suggests that the optical band gap of degenerately doped semiconductors increases when all states close to the conduction band get populated due to shifting of an absorption edge to higher energy, is important, as it gives a chance to obtain different optical properties for the same material. Here, we report our observations of the similar shift in the optical band gap in NixFe2−xO3 nanocomposites as a function of composition with the help of cyclic voltammetry (CV) and XPS valence band (VB) position measurements. The conduction band edge (CBE) position of the NixFe2−xO3 nanocomposites as determined using CV was noted to move towards more negative potential with increasing Ni-concentration. A similar shift is also noted in the CBE estimated using XPS measurements (by subtracting the VB position from the optical band gap values). The observed shift in the optical band gap along with the CBE position gives the corresponding shift in the Fermi level, which is found to move closer to the CBE position, suggesting the observation of an effect similar to the B–M shift. Also, the extent of band bending estimated from the deviation of the CBE from the flat band potential (measured through Mott–Schottky plots) is found to increase with increasing Ni-concentration. Moreover, the Ni-composition has been observed to enhance the current density as well as to facilitate water splitting at a much lower onset potential compared to pure hematite. The NixFe2−xO3 nanocomposite with an 11 mol% Ni-composition shows the highest photo-electrochemical response with an almost ten times enhancement in the current density at 1.9 V vs. RHE in alkaline medium, as compared to the dark current. This enhanced performance is attributed to the improved charge separation and higher charge carrier density as a result of the higher extent of band bending in the NixFe2−xO3 nanocomposites.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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