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Journal ArticleDOI

Forming heterojunction: an effective strategy to enhance the photocatalytic efficiency of a new metal-free organic photocatalyst for water splitting.

29 Jul 2016-Scientific Reports (Nature Publishing Group)-Vol. 6, Iss: 1, pp 29327-29327
TL;DR: This article provides a metal-free organic photocatalyst g-C12N7H3 for water splitting, and proposes a good strategy- forming heterojunction, which can effectively improve the electron-hole separation, and provides four strategies to enhance the photocatalytic efficiency.
Abstract: Photocatalytic water splitting is a new technology for the conversion and utilization of solar energy and has a potential prospect. One important aspect of enhancing the photocatalytic efficiency is how to improve the electron-hole separation. Up to now, there is still no ideal strategy to improve the electron-hole separation. In this article, for metal-free organic photocatalysts, we propose a good strategy- forming heterojunction, which can effectively improve the electron-hole separation. We provide a metal-free organic photocatalyst g-C12N7H3 for water splitting. The stability of g-C12N7H3 has been investigated, the X-ray diffraction spectra has been simulated. Using first-principles calculations, we have systematically studied the electronic structure, band edge alignment, and optical properties for the g-C12N7H3. The results demonstrated that g-C12N7H3 is a new organocatalyst material for water splitting. In order to enhance the photocatalytic efficiency, we provided four strategies, i.e., multilayer stacking, raising N atoms, forming g-C9N10/g-C12N7H3 heterojunction, and forming graphene/g-C12N7H3 heterojunction. Our research is expected to stimulate experimentalists to further study novel 2D metal-free organic materials as visible light photocatalysts. Our strategies, especially forming heterojunction, will substantially help to enhance the photocatalytic efficiency of metal-free organic photocatalyst.

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Citations
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Journal ArticleDOI
TL;DR: In this article, the authors summarized the recent advances in 2D carbonaceous photocatalysts with respect to physicochemical and photochemical tuning for solar light mediated hydrogen evolution and showed that the feasibility of structural and chemical modification to optimize visible light absorption and charge separation makes carbonaceous semiconductors promising candidates to convert solar energy into chemical energy.
Abstract: The overwhelming challenge of depleting fossil fuels and anthropogenic carbon emissions has driven research into alternative clean sources of energy. To achieve the goal of a carbon neutral economy, the harvesting of sunlight by using photocatalysts to split water into hydrogen and oxygen is an expedient approach to fulfill the energy demand in a sustainable way along with reducing the emission of greenhouse gases. Even though the past few decades have witnessed intensive research into inorganic semiconductor photocatalysts, their quantum efficiencies for hydrogen production from visible photons remain too low for the large scale deployment of this technology. Visible light absorption and efficient charge separation are two key necessary conditions for achieving the scalable production of hydrogen from water. Two-dimensional carbon based nanoscale materials such as graphene oxide, reduced graphene oxide, carbon nitride, modified 2D carbon frameworks and their composites have emerged as potential photocatalysts due to their astonishing properties such as superior charge transport, tunable energy levels and bandgaps, visible light absorption, high surface area, easy processability, quantum confinement effects, and high photocatalytic quantum yields. The feasibility of structural and chemical modification to optimize visible light absorption and charge separation makes carbonaceous semiconductors promising candidates to convert solar energy into chemical energy. In the present review, we have summarized the recent advances in 2D carbonaceous photocatalysts with respect to physicochemical and photochemical tuning for solar light mediated hydrogen evolution.

198 citations

Journal ArticleDOI
TL;DR: In this article, the performance of photocatalysts is evaluated in terms of quantum yield, space-time yield, and other operational variables, including mode of operation, irradiation time, and relative humidity.
Abstract: Hydrogen sulfide (H2S) is regarded as a broad-spectrum poison associated with severe health consequences. Among the available treatment options, photocatalytic technology may be effectively applied to the production of hydrogen gas through the splitting of H2S molecules and the addition of 79.9 kJ mol−1 of energy. As a result, advanced photo-reactive media may provide a win-win strategy to treat the parent pollutant (H2S) while producing hydrogen gas. This review encompasses both TiO2 and non-TiO2 catalysts capable of operating under ultraviolet, visible, and solar light irradiation. The performances of photocatalysts are assessed in terms of quantum yield, space-time yield, and other operational variables, including mode of operation, irradiation time, and relative humidity. The concept of space velocity is used to compare photocatalysts in reference to benchmark parameters for the treatment of H2S. This review addresses current limitations and future prospects of the application of photocatalytic technology to efficiently mitigate H2S pollution.

68 citations

Journal ArticleDOI
TL;DR: In this article, the authors provide a complete survey on both layered TMDC and non-layered transition metal dichalcogenides (TMC) co-catalysts on Si photoelectrodes.
Abstract: In the photoelectrochemical (PEC) water splitting (WS) reactions, a photon is absorbed by a semiconductor, generating electron-hole pairs which are transferred across the semiconductor/electrolyte interface to reduce or oxidize water into oxygen or hydrogen. Catalytic junctions are commonly combined with semiconductor absorbers, providing electrochemically active sites for charge transfer across the interface and increasing the surface band bending to improve the PEC performance. In this review, we focus on transition metal (di)chalcogenide [TM(D)C] catalysts in conjunction with silicon photoelectrode as Earth-abundant materials systems. Surprisingly, there is a limited number of reports in Si/TM(D)C for PEC WS in the literature. We provide almost a complete survey on both layered TMDC and non-layered transition metal dichalcogenides (TMC) co-catalysts on Si photoelectrodes, mainly photocathodes. The mechanisms of the photovoltaic power conversion of silicon devices are summarized with emphasis on the exact role of catalysts. Diverse approaches to the improved PEC performance and the proposed synergetic functions of catalysts on the underlying Si are reviewed. Atomic layer deposition of TM(D)C materials as a new methodology for directly growing them and its implication for low-temperature growth on defect chemistry are featured. The multi-phase TM(D)C overlayers on Si and the operation principles are highlighted. Finally, challenges and directions regarding future research for achieving the theoretical PEC performance of Si-based photoelectrodes are provided.

47 citations

Journal ArticleDOI
TL;DR: Besides its high catalytic activity, the mpg-CN/BP-AgPd nanocomposites were reusable catalysts in the methanolysis of AB.
Abstract: A novel ternary nanocomposite, mesoporous graphitic carbon nitride/black phosphorus-AgPd (denoted mpg-CN/BP-AgPd), was successfully fabricated by assembling the as-prepared AgPd alloy nanoparticles (NPs) on mesoporous graphitic carbon nitride/black phosphorus (mpg-CN/BP) binary composites. This novel nanocomposite comprises a heterojunction support material formed by two distinct nonmetallic semiconductors (mpg-CN and BP) with adaptable band gaps and edge voltages, providing enhanced catalytic activity to AgPd alloy NPs in hydrogen generation from the methanolysis of ammonia borane (AB) compared to its single components under the blue light-emitting diode (LED) light illumination. The yielded mpg-CN/BP-AgPd ternary nanocomposites were characterized by many advanced analytical techniques (transmission electron microscopy (TEM), high-resolution TEM (HR-TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), photoluminescence spectroscopy (PL), time-resolved spectroscopy, inductively coupled plasma-mass spectroscopy (ICP-MS), and fourier transform infrared (FTIR), and then they were tested as catalysts in hydrogen generation from the methanolysis of AB at room temperature. Several parameters such as the effect of mpg-CN/BP ratio, alloy composition, and type of the light source were studied to optimize the catalytic activity of the mpg-CN/BP-AgPd nanocomposites in the methanolysis of AB. The best catalytic activity of mpg-CN/BP-AgPd nanocomposites was obtained using an mpg-CN/BP ratio of 5/1 (wt/wt) and Ag50Pd50 alloy composition under the blue LED illumination at room temperature. The activity of the ternary nanocomposites was further enhanced by the acetic acid treatment, and a high initial turnover frequency of 43.7 mol(H2) mol(catalyst)-1 min-1 was reported. Besides their high catalytic activity, the mpg-CN/BP-AgPd nanocomposites were reusable catalysts in the methanolysis of AB. This study also included detailed kinetics of AB methanolysis catalyzed by mpg-CN/BP-AgPd nanocomposites.

45 citations

Journal ArticleDOI
TL;DR: In this article, first principles calculations based on density functional theory with generalized gradient approximation were used to investigate and compare the structural, electronic and optical properties of two photoanode materials for use in photocatalytic water splitting.

43 citations

References
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Journal ArticleDOI
TL;DR: A simple derivation of a simple GGA is presented, in which all parameters (other than those in LSD) are fundamental constants, and only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked.
Abstract: Generalized gradient approximations (GGA’s) for the exchange-correlation energy improve upon the local spin density (LSD) description of atoms, molecules, and solids. We present a simple derivation of a simple GGA, in which all parameters (other than those in LSD) are fundamental constants. Only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked. Improvements over PW91 include an accurate description of the linear response of the uniform electron gas, correct behavior under uniform scaling, and a smoother potential. [S0031-9007(96)01479-2] PACS numbers: 71.15.Mb, 71.45.Gm Kohn-Sham density functional theory [1,2] is widely used for self-consistent-field electronic structure calculations of the ground-state properties of atoms, molecules, and solids. In this theory, only the exchange-correlation energy EXC › EX 1 EC as a functional of the electron spin densities n"srd and n#srd must be approximated. The most popular functionals have a form appropriate for slowly varying densities: the local spin density (LSD) approximation Z d 3 rn e unif

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81,985 citations

Journal ArticleDOI
Peter E. Blöchl1
TL;DR: An approach for electronic structure calculations is described that generalizes both the pseudopotential method and the linear augmented-plane-wave (LAPW) method in a natural way and can be used to treat first-row and transition-metal elements with affordable effort and provides access to the full wave function.
Abstract: An approach for electronic structure calculations is described that generalizes both the pseudopotential method and the linear augmented-plane-wave (LAPW) method in a natural way. The method allows high-quality first-principles molecular-dynamics calculations to be performed using the original fictitious Lagrangian approach of Car and Parrinello. Like the LAPW method it can be used to treat first-row and transition-metal elements with affordable effort and provides access to the full wave function. The augmentation procedure is generalized in that partial-wave expansions are not determined by the value and the derivative of the envelope function at some muffin-tin radius, but rather by the overlap with localized projector functions. The pseudopotential approach based on generalized separable pseudopotentials can be regained by a simple approximation.

61,450 citations

Journal ArticleDOI
TL;DR: In this paper, the formal relationship between US Vanderbilt-type pseudopotentials and Blochl's projector augmented wave (PAW) method is derived and the Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional.
Abstract: The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Bl\"ochl's projector augmented wave (PAW) method is derived. It is shown that the total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addition, critical tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed core all electron methods. These tests include small molecules $({\mathrm{H}}_{2}{,\mathrm{}\mathrm{H}}_{2}{\mathrm{O},\mathrm{}\mathrm{Li}}_{2}{,\mathrm{}\mathrm{N}}_{2}{,\mathrm{}\mathrm{F}}_{2}{,\mathrm{}\mathrm{BF}}_{3}{,\mathrm{}\mathrm{SiF}}_{4})$ and several bulk systems (diamond, Si, V, Li, Ca, ${\mathrm{CaF}}_{2},$ Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.

57,691 citations

Journal ArticleDOI
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