Abstract: Electron-hole recombination and photocorrosion are two challenges that seriously limit the application of two-dimensional (2D) transition metal dichalcogenides (TMDs) for photocatalytic water splitting. In this work, we propose a 2D van der Waals MoSe2/Ti2CO2 heterojunction that features promising resistance to both electron-hole recombination and photocorrosion existing in TMDs. By means of first-principles calculations, the MoSe2/Ti2CO2 heterojunction is demonstrated to be a direct Z-scheme photocatalyst for overall water splitting with MoSe2 and Ti2CO2 serving as photocatalysts for hydrogen and oxygen evolution reactions, respectively, which is beneficial to electron-hole separation. The ultrafast migration of photo-generated holes from MoSe2 to Ti2CO2 as well as the anti-photocorrosion ability of Ti2CO2 are responsible for photocatalytic stability. This heterojunction is experimentally reachable and exhibits a high solar-to-hydrogen efficiency of 12%. The strategy proposed here paves the way for developing 2D photocatalysts for water splitting with high performance and stability in experiments.

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Topics: Photocatalytic water splitting (56%), Water splitting (56%), Heterojunction (54%)

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10 results found

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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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Topics: van der Waals force (52%)

48 Citations

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Abstract: In this study, we propose an innovative Hf2CO2/WS2 heterostructure with excellent photocatalytic performance for water splitting based on first-principles calculations. The binding energy, and ab initio molecular dynamics (AIMD) simulations exhibit this material's excellent ambient stability. Furthermore, the band structure confirms that the Hf2CO2/WS2 heterostructure possesses the intrinsic type-II semiconductor and are well satisfied with the requirements of redox energy level in water splitting reaction. Meanwhile, the charge transfer occurs from Hf2CO2 to WS2 monolayer, which further induces the separation of photogenerated carriers and prolong the lifetime of carriers. Dramatically high visible-light absorption (~6.3 × 105 cm−1) and carrier mobility (~2.2 × 103 cm2 V-1 s-1) are found, which means that the heterostructure has adequate motive force to make the photogenerated carriers separate into different monolayers quickly before recombination. Moreover, according to Gibbs free energy calculation, HER and OER can be triggered spontaneously under the driving of external potential. The results confirm that the thermodynamic feasibility of water splitting on Hf2CO2/WS2 heterostructure surface. Hence, these distinctive features endow Hf2CO2/WS2 heterostructure with the potential ability of photocatalytic water splitting, which provides a potential avenue for the future experimental project.

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Topics: Water splitting (54%), Photocatalytic water splitting (54%), Heterojunction (52%) ... show more

2 Citations

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Abstract: Enabled by electron donor-acceptor complexes, a novel visible-light-induced α-amino C-H bond arylation protocol, without a photoredox catalyst, has been disclosed. The protocol does not require any transition metal, oxidant, or exclusion of oxygen or moisture. A direct irradiation of the mixture of tertiary amines and benzonitriles with visible light in N,N-diethylethanamide in the presence of Cs2CO3 afforded α-arylated amines in good to excellent yields.

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Topics: Electron donor (59%), Acceptor (52%), Catalysis (51%)

1 Citations

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Abstract: Two-dimensional (2D) materials with unique structures and fascinating photoelectric properties are typically employed as supporting materials but they have not been mentioned in the context of polarity-reversal-mode photoelectrochemical (PEC) biosensors. Herein, a novel 2D Ti2C MXene-induced photocurrent polarity switching PEC biosensing platform was constructed for the selective and ultrasensitive detection of soluble CD146 (sCD146). Ag2S quantum dots (QDs)-fixed indium-tin oxide slices were used as the photocathode electrodes, and the capture antibody (Ab1) was assembled on the electrode. When the target sCD146 existed, 2D Ti2C MXene labeled with the detection antibody (Ab2) was introduced onto the modified electrode through a typical antigen-antibody sandwich immune reaction, resulting in a polarity switch from a cathodic to an anodic photocurrent. The outstanding optical and electron-transfer capability of the 2D Ti2C MXene made it beneficial to establish a high-performance photocurrent polarity switching PEC biosensor for sCD146 assay, and a linear response range of 0.1–1000 pg/mL with a detection limit of 18 fg/mL was obtained. Furthermore, the developed PEC biosensing strategy possessed excellent anti-interference ability for precluding the false positive or negative signals. The designed 2D Ti2C MXene opens up a new two-dimensional photocurrent-polarity switcher for constructing high-performance PEC biosensors, and the environmentally friendly 2D Ti2C MXene//Ag2S QDs photocurrent polarity switching system could overcome the harmfulness of conventional toxic semiconductors for operators and the environment, offering great potential applications in biological analysis and disease diagnosis.

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Topics: Photocurrent (53%)

1 Citations

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Abstract: Bismuth vanadate (BiVO4) has been one of the most extensively investigated materials in photocatalytic fields owing to its low cost and high performance. Despite much available evidences about its band alignment and photogenerated carrier migration, a convincing explanation of how photogenerated carrier migration occurs in its polymorph phase junction as well as its exact electronic structure has remained elusive. Herein, we designed a high-quality hierarchical tzBiVO4/msBiVO4 phase junction to elucidate the photogenerated carrier migration process and its correlated band alignment. Via the X-ray photoelectron spectroscopy (XPS) and the density functional theory (DFT) calculations, we unveil that a particular band alignment containing Z-scheme and type-II features exists between tzBiVO4 and msBiVO4, where the tzBiVO4 component in tzBiVO4/msBiVO4 showing a higher collecting and oxidizing ability of the photogenerated holes at the designed interface. Importantly, this study offers a new understanding of the BiVO4 atomistic nature of bonding, electronic structure and their related photocatalytic nature.

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1 Citations

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60 results found

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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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Topics: Local-density approximation (60%), Orbital-free density functional theory (57%), Density functional theory (56%) ... show more

117,932 Citations

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Abstract: We present an efficient scheme for calculating the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set. In the first part the application of Pulay's DIIS method (direct inversion in the iterative subspace) to the iterative diagonalization of large matrices will be discussed. Our approach is stable, reliable, and minimizes the number of order ${\mathit{N}}_{\mathrm{atoms}}^{3}$ operations. In the second part, we will discuss an efficient mixing scheme also based on Pulay's scheme. A special ``metric'' and a special ``preconditioning'' optimized for a plane-wave basis set will be introduced. Scaling of the method will be discussed in detail for non-self-consistent and self-consistent calculations. It will be shown that the number of iterations required to obtain a specific precision is almost independent of the system size. Altogether an order ${\mathit{N}}_{\mathrm{atoms}}^{2}$ scaling is found for systems containing up to 1000 electrons. If we take into account that the number of k points can be decreased linearly with the system size, the overall scaling can approach ${\mathit{N}}_{\mathrm{atoms}}$. We have implemented these algorithms within a powerful package called VASP (Vienna ab initio simulation package). The program and the techniques have been used successfully for a large number of different systems (liquid and amorphous semiconductors, liquid simple and transition metals, metallic and semiconducting surfaces, phonons in simple metals, transition metals, and semiconductors) and turned out to be very reliable. \textcopyright{} 1996 The American Physical Society.

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Topics: DIIS (51%)

64,484 Citations

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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.

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Topics: Projector augmented wave method (66%), Pseudopotential (58%)

48,474 Citations

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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.

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Topics: Cauchy stress tensor (53%)

46,297 Citations

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Abstract: We present a detailed description and comparison of algorithms for performing ab-initio quantum-mechanical calculations using pseudopotentials and a plane-wave basis set. We will discuss: (a) partial occupancies within the framework of the linear tetrahedron method and the finite temperature density-functional theory, (b) iterative methods for the diagonalization of the Kohn-Sham Hamiltonian and a discussion of an efficient iterative method based on the ideas of Pulay's residual minimization, which is close to an order Natoms2 scaling even for relatively large systems, (c) efficient Broyden-like and Pulay-like mixing methods for the charge density including a new special ‘preconditioning’ optimized for a plane-wave basis set, (d) conjugate gradient methods for minimizing the electronic free energy with respect to all degrees of freedom simultaneously. We have implemented these algorithms within a powerful package called VAMP (Vienna ab-initio molecular-dynamics package). The program and the techniques have been used successfully for a large number of different systems (liquid and amorphous semiconductors, liquid simple and transition metals, metallic and semi-conducting surfaces, phonons in simple metals, transition metals and semiconductors) and turned out to be very reliable.

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Topics: Projector augmented wave method (55%), Conjugate gradient method (55%), Iterative method (54%) ... show more

40,008 Citations