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Journal ArticleDOI

TM3 (TM = V, Fe, Mo, W) single-cluster catalyst confined on porous BN for electrocatalytic nitrogen reduction

TL;DR: In this article, the catalytic activity of a triplet form of transition-metal single-clusters in the surface cavities of porous boron nitride (p-BN) nanosheets was investigated.
About: This article is published in Journal of Materials Science & Technology.The article was published on 2022-05-10. It has received 11 citations till now. The article focuses on the topics: Catalysis & Electrocatalyst.
Citations
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Journal ArticleDOI
TL;DR: In this paper , a comprehensive review of electrochemical and photochemical nitrogen reduction reaction (NRR) activities and selectivities of various supported single-atom and polyatomic cluster catalysts is presented.
Abstract: Fixation of dinitrogen into ammonia is an essential biological process for the evolution of life, and at the same time ammonia is an essential component for many industrial processes, including fertilizers, plastics, and so on. NH3 is also known as the best alternative to H2 in fuel cells. However, due to chemical inertness, direct conversion of N2 into NH3 is not possible; a suitable catalyst is required. The century-old Haber–Bosch process, utilizing an Fe-based catalyst, is extremely energy-intensive and eco-unfriendly due to the consumption of fossil fuels. In recent years, huge development has taken place in the design and applications of suitable electro- and photocatalysts for artificial N2 fixation. First-principles calculations have been considered as a powerful avenue for theoretical screening of promising catalysts through rational design and analysis of the plausible mechanisms or pathways of reactions. The present review focuses on recent theoretical developments of various unsupported nanoclusters and supported single-atom and cluster catalysts for application in electro- and photochemical N2 reduction reactions. The support substrates include oxides, carbides, nitrides of metal-based 2D materials, porous carbonaceous materials, and metal-free 2D materials containing main-group elements like B, C, N, and P. Although some reviews have already been made, focusing on the research related to either electro- or photocatalytic N2 fixation on different catalysts, here we give a comprehensive account of both electrochemical and photochemical nitrogen reduction reaction (NRR) activities and selectivities of various supported single-atom and polyatomic cluster catalysts. Additionally, a comparative assessment is made on the basis of free energy of adsorption, most favorable pathway, potential limiting step, and corresponding limiting potential of the NRR.

9 citations

Journal ArticleDOI
TL;DR: In this article , an efficient strategy by atomic spin regulation to promote nitrogen reduction reaction through Fe-transition metal (TM) hybrid heteronuclear dual-atom catalysts has been studied, and the stability, activity and selectivity of 30 kinds of Fe-based dual-atoms anchored on N-doped porous graphene are systematically investigated to evaluate their catalytic performance.

5 citations

Journal ArticleDOI
TL;DR: In this paper , the recent progress of Fe-based electrocatalysts and their coordination effect, synergistic effect and defect effect for nitrogen reduction reaction have been summarized and discussed.

4 citations

Journal ArticleDOI
TL;DR: In this paper , the authors investigated CO oxidation pathways over SACs in reaction conditions using atomically dispersed Au on h-BN (AuBN) as a model with extensive first-principles-based calculations and demonstrated that the adsorption of reactants, namely CO, O2 and CO2, and their coadsorption with reaction species on AuBN would lead to various reaction species with different reactivity and impact the CO conversion.
Abstract: Similar to the metal centers in biocatalysis and homogeneous catalysis, the metal species in single atom catalysts (SACs) are charged, atomically dispersed and stabilized by support and substrate. The reaction condition dependent catalytic performance of SACs has long been realized, but seldom investigated before. We investigated CO oxidation pathways over SACs in reaction conditions using atomically dispersed Au on h-BN (AuBN) as a model with extensive first-principles-based calculations. We demonstrated that the adsorption of reactants, namely CO, O2 and CO2, and their coadsorption with reaction species on AuBN would be condition dependent, leading to various reaction species with different reactivity and impact the CO conversion. Specifically, the revised Langmuir–Hinshelwood pathway with the CO-mediated activation of O2 and dissociation of cyclic peroxide intermediate followed by the Eley–Rideal type reduction is dominant at high temperatures, while the coadsorbed CO-mediated dissociation of peroxide intermediate becomes plausible at low temperatures and high CO partial pressures. Carbonate species would also form in existence of CO2, react with coadsorbed CO and benefit the conversion. The findings highlight the origin of the condition-dependent CO oxidation performance of SACs in detailed conditions and may help to rationalize the current understanding of the superior catalytic performance of SACs.

4 citations

Journal ArticleDOI
TL;DR: In this paper , the authors take the cohesive energy property of metal (Ec) as the descriptor, and find the high-performance atomically dispersed catalyst by rationally locating the catalyst.
Abstract: To rationally locate the high-performance atomically dispersed catalyst remains a challenge, albeit wide explorations in numerous critical chemical reactions. Here, taking the cohesive-energy property of metal (Ec) as the descriptor,...

3 citations

References
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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 authors present an ab initio quantum-mechanical molecular-dynamics calculations based on the calculation of the electronic ground state and of the Hellmann-Feynman forces in the local density approximation.
Abstract: We present ab initio quantum-mechanical molecular-dynamics calculations based on the calculation of the electronic ground state and of the Hellmann-Feynman forces in the local-density approximation at each molecular-dynamics step. This is possible using conjugate-gradient techniques for energy minimization, and predicting the wave functions for new ionic positions using subspace alignment. This approach avoids the instabilities inherent in quantum-mechanical molecular-dynamics calculations for metals based on the use of a fictitious Newtonian dynamics for the electronic degrees of freedom. This method gives perfect control of the adiabaticity and allows us to perform simulations over several picoseconds.

32,798 citations

Journal ArticleDOI
TL;DR: A way is found to visualize and understand the nonlocality of exchange and correlation, its origins, and its physical effects as well as significant interconfigurational and interterm errors remain.
Abstract: Generalized gradient approximations (GGA's) seek to improve upon the accuracy of the local-spin-density (LSD) approximation in electronic-structure calculations. Perdew and Wang have developed a GGA based on real-space cutoff of the spurious long-range components of the second-order gradient expansion for the exchange-correlation hole. We have found that this density functional performs well in numerical tests for a variety of systems: (1) Total energies of 30 atoms are highly accurate. (2) Ionization energies and electron affinities are improved in a statistical sense, although significant interconfigurational and interterm errors remain. (3) Accurate atomization energies are found for seven hydrocarbon molecules, with a rms error per bond of 0.1 eV, compared with 0.7 eV for the LSD approximation and 2.4 eV for the Hartree-Fock approximation. (4) For atoms and molecules, there is a cancellation of error between density functionals for exchange and correlation, which is most striking whenever the Hartree-Fock result is furthest from experiment. (5) The surprising LSD underestimation of the lattice constants of Li and Na by 3--4 % is corrected, and the magnetic ground state of solid Fe is restored. (6) The work function, surface energy (neglecting the long-range contribution), and curvature energy of a metallic surface are all slightly reduced in comparison with LSD. Taking account of the positive long-range contribution, we find surface and curvature energies in good agreement with experimental or exact values. Finally, a way is found to visualize and understand the nonlocality of exchange and correlation, its origins, and its physical effects.

17,848 citations

Journal ArticleDOI
TL;DR: The simulation allows us to study in detail the changes in the structure-property relationship through the metal-semiconductor transition, and a detailed analysis of the local structural properties and their changes induced by an annealing process is reported.
Abstract: We present ab initio quantum-mechanical molecular-dynamics simulations of the liquid-metal--amorphous-semiconductor transition in Ge. Our simulations are based on (a) finite-temperature density-functional theory of the one-electron states, (b) exact energy minimization and hence calculation of the exact Hellmann-Feynman forces after each molecular-dynamics step using preconditioned conjugate-gradient techniques, (c) accurate nonlocal pseudopotentials, and (d) Nos\'e dynamics for generating a canonical ensemble. This method gives perfect control of the adiabaticity of the electron-ion ensemble and allows us to perform simulations over more than 30 ps. The computer-generated ensemble describes the structural, dynamic, and electronic properties of liquid and amorphous Ge in very good agreement with experiment. The simulation allows us to study in detail the changes in the structure-property relationship through the metal-semiconductor transition. We report a detailed analysis of the local structural properties and their changes induced by an annealing process. The geometrical, bonding, and spectral properties of defects in the disordered tetrahedral network are investigated and compared with experiment.

16,744 citations

Journal ArticleDOI
TL;DR: Density functional theory calculations explain copper's unique ability to convert CO2 into hydrocarbons, which may open up (photo-)electrochemical routes to fuels as mentioned in this paper, which may lead to new energy sources.
Abstract: Density functional theory calculations explain copper's unique ability to convert CO2 into hydrocarbons, which may open up (photo-)electrochemical routes to fuels.

2,420 citations