Journal Article•
Direct Z-Scheme Water Splitting Photocatalyst Based on Two-Dimensional Van Der Waals Heterostructures
TL;DR: The results prove that the 2D vdW heterostructure family is convincing for a new type of direct Z-scheme photocatalysts searching, based on time-dependent ab initio nonadiabatic molecular dynamics investigation.
Abstract: Mimicking the natural photosynthesis in plants, Z-scheme water splitting is a promising strategy to improve photocatalytic activity. Searching for the direct Z-scheme photocatalysts is urgent and the crucial factor for the photocatalytic efficiency is the photogenerated electron-hole ( e-h) recombination rate at the interface of two photosystems. In this report, based on time-dependent ab initio nonadiabatic molecular dynamics (NAMD) investigation, we first report a two-dimensional (2D) metal-free van der Waals (vdW) heterostructure consisting of monolayer BCN and C2N as a promising candidate for direct Z-scheme photocatalysts for water splitting. It is shown that the time scale of e-h recombination of BCN/C2N is within 2 ps. Among such e-h recombination events, more than 85% are through the e-h recombination at the interface. NAMD simulations based on frozen phonon method prove that such an ultrafast interlayer e-h recombination is assisted by intralayer optical phonon modes and the interlayer shear phonon mode induced by vdW interaction. In these crucial phonon modes, the interlayer relative movements which are lacking in traditional heterostructures with strong interactions, yet exist generally in various 2D vdW heterostructures, are significant. Our results prove that the 2D vdW heterostructure family is convincing for a new type of direct Z-scheme photocatalysts searching.
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01 Jan 2021
332 citations
TL;DR: Aiming to enhance the photocatalytic performance, general strategies of materials design are discussed, including codoping and introducing a built-in electric field to improve the light harvesting of materials and constructing heterojunctions to enhance light harvesting and electron-hole separation.
Abstract: Currently, problems associated with energy and environment have become increasingly serious. Producing hydrogen, a clean and renewable resource, through photocatalytic water splitting using solar energy is a feasible and efficient route for resolving these problems, and great efforts have been devoted to improve the solar-to-hydrogen efficiency. Light harvesting and electron-hole separation are key in enhancing the efficiency of solar energy utilization, which stimulates the development of new photocatalytic materials. Here, recent advances in material design for photocatalytic water splitting are presented from a theoretical perspective. Specifically, aiming to enhance the photocatalytic performance, general strategies of materials design are discussed, including codoping and introducing a built-in electric field to improve the light harvesting of materials, reducing the dimension of materials to shorten the migration pathway of carriers to inhibit electron-hole recombination, and constructing heterojunctions to enhance light harvesting and electron-hole separation. Future opportunities and challenges in the theoretical design of photocatalytic materials toward water splitting are also included.
222 citations
193 citations
TL;DR: This work intends to provide a comprehensive and timely review on direct Z-scheme photocatalysts from the material’s point of view and is expected that the insights of this up-to-date review could guide the material design and performance improvement of the direct Z -scheme systems to achieve their maximum potentials.
154 citations
TL;DR: The OER of water splitting is a thermodynamically permissible reaction without the aid of any other substance, which indicates that InSe/ g-C3N4 is an excellent candidate for photocatalyst or photoelectronic applications.
Abstract: We propose a conceptual design of InSe/g-C3N4 van der Waals heterostructure to achieve highly efficient and spontaneous water splitting. InSe/g-C3N4 possesses a direct band gap of 2.04 eV with type-II band alignment, which is beneficial to the separation of electrons and holes and exhibits proper valence and conduction-band positions for the redox reactions of H2O. In addition, the adsorption of multiple water molecules and the changes of free energy on InSe/g-C3N4 have been calculated to understand the oxygen evolution reaction (OER) process of water splitting. The free energies of reaction on three sides are all downhill, and the values of ΔG reduce to about −0.406 eV, indicating that the OER of water splitting is a thermodynamically permissible reaction without the aid of any other substance. Therefore, the water-splitting reaction could be thermodynamically continued using InSe/g-C3N4 as a photocatalyst, which indicates that InSe/g-C3N4 is an excellent candidate for photocatalyst or photoelectronic ap...
142 citations
References
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TL;DR: A detailed description and comparison of algorithms for performing ab-initio quantum-mechanical calculations using pseudopotentials and a plane-wave basis set is presented in this article. But this is not a comparison of our algorithm with the one presented in this paper.
47,666 citations
TL;DR: Water photolysis is investigated by exploiting the fact that water is transparent to visible light and cannot be decomposed directly, but only by radiation with wavelengths shorter than 190 nm.
Abstract: ALTHOUGH the possibility of water photolysis has been investigated by many workers, a useful method has only now been developed. Because water is transparent to visible light it cannot be decomposed directly, but only by radiation with wavelengths shorter than 190 nm (ref. 1).
27,819 citations
TL;DR: A new density functional of the generalized gradient approximation (GGA) type for general chemistry applications termed B97‐D is proposed, based on Becke's power‐series ansatz from 1997, and is explicitly parameterized by including damped atom‐pairwise dispersion corrections of the form C6 · R−6.
Abstract: A new density functional (DF) of the generalized gradient approximation (GGA) type for general chemistry applications termed B97-D is proposed. It is based on Becke's power-series ansatz from 1997 and is explicitly parameterized by including damped atom-pairwise dispersion corrections of the form C(6) x R(-6). A general computational scheme for the parameters used in this correction has been established and parameters for elements up to xenon and a scaling factor for the dispersion part for several common density functionals (BLYP, PBE, TPSS, B3LYP) are reported. The new functional is tested in comparison with other GGAs and the B3LYP hybrid functional on standard thermochemical benchmark sets, for 40 noncovalently bound complexes, including large stacked aromatic molecules and group II element clusters, and for the computation of molecular geometries. Further cross-validation tests were performed for organometallic reactions and other difficult problems for standard functionals. In summary, it is found that B97-D belongs to one of the most accurate general purpose GGAs, reaching, for example for the G97/2 set of heat of formations, a mean absolute deviation of only 3.8 kcal mol(-1). The performance for noncovalently bound systems including many pure van der Waals complexes is exceptionally good, reaching on the average CCSD(T) accuracy. The basic strategy in the development to restrict the density functional description to shorter electron correlation lengths scales and to describe situations with medium to large interatomic distances by damped C(6) x R(-6) terms seems to be very successful, as demonstrated for some notoriously difficult reactions. As an example, for the isomerization of larger branched to linear alkanes, B97-D is the only DF available that yields the right sign for the energy difference. From a practical point of view, the new functional seems to be quite robust and it is thus suggested as an efficient and accurate quantum chemical method for large systems where dispersion forces are of general importance.
23,058 citations
TL;DR: The slow pace of hazardous waste remediation at military installations around the world is causing a serious delay in conversion of many of these facilities to civilian uses as discussed by the authors, which is a serious problem.
Abstract: The civilian, commercial, and defense sectors of most advanced industrialized nations are faced with a tremendous set of environmental problems related to the remediation of hazardous wastes, contaminated groundwaters, and the control of toxic air contaminants. For example, the slow pace of hazardous waste remediation at military installations around the world is causing a serious delay in conversion of many of these facilities to civilian uses. Over the last 10 years problems related to hazardous waste remediation have emerged as a high national and international priority.
17,188 citations
TL;DR: In this paper, a new hybrid density functional based on a screened Coulomb potential for the exchange interaction is proposed, which enables fast and accurate hybrid calculations, even of usually difficult metallic systems.
Abstract: Hybrid density functionals are very successful in describing a wide range of molecular properties accurately. In large molecules and solids, however, calculating the exact (Hartree–Fock) exchange is computationally expensive, especially for systems with metallic characteristics. In the present work, we develop a new hybrid density functional based on a screened Coulomb potential for the exchange interaction which circumvents this bottleneck. The results obtained for structural and thermodynamic properties of molecules are comparable in quality to the most widely used hybrid functionals. In addition, we present results of periodic boundary condition calculations for both semiconducting and metallic single wall carbon nanotubes. Using a screened Coulomb potential for Hartree–Fock exchange enables fast and accurate hybrid calculations, even of usually difficult metallic systems. The high accuracy of the new screened Coulomb potential hybrid, combined with its computational advantages, makes it widely applicable to large molecules and periodic systems.
13,446 citations