scholarly journals Mo-doped boron nitride monolayer as a promising single-atom electrocatalyst for CO2 conversion

2019 ◽  
Vol 10 ◽  
pp. 540-548 ◽  
Author(s):  
Qianyi Cui ◽  
Gangqiang Qin ◽  
Weihua Wang ◽  
Lixiang Sun ◽  
Aijun Du ◽  
...  
Keyword(s):  
Boron Nitride ◽  
Density Functional ◽  
Experimental Studies ◽  
Catalytic Performance ◽  
Reduction Reaction ◽  
Single Atom ◽  
Ambient Conditions ◽  
Functional Theory ◽  
Earth Abundant ◽  
Insight Into

The design of new, efficient catalysts for the conversion of CO2 to useful fuels under mild conditions is urgent in order to reduce greenhouse gas emissions and alleviate the energy crisis. In this work, a series of transition metals (TMs), including Sc to Zn, Mo, Ru, Rh, Pd and Ag, supported on a boron nitride (BN) monolayer with boron vacancies, were investigated as electrocatalysts for the CO2 reduction reaction (CRR) using comprehensive density functional theory (DFT) calculations. The results demonstrate that a single-Mo-atom-doped boron nitride (Mo-doped BN) monolayer possesses excellent performance for converting CO2 to CH4 with a relatively low limiting potential of −0.45 V, which is lower than most catalysts for the selective production of CH4 as found in both theoretical and experimental studies. In addition, the formation of OCHO on the Mo-doped BN monolayer in the early hydrogenation steps is found to be spontaneous, which is distinct from the conventional catalysts. Mo, as a non-noble element, presents excellent catalytic performance with coordination to the BN monolayer, and is thus a promising transition metal for catalyzing CRR. This work not only provides insight into the mechanism of CRR on the single-atom catalyst (Mo-doped BN monolayer) at the atomic level, but also offers guidance in the search for appropriate earth-abundant TMs as electrochemical catalysts for the efficient conversion of CO2 to useful fuels under ambient conditions.

Two-dimensional metal-organic frameworks Mo3(C2O)12 as promising single-atom catalysts for selective nitrogen-to-ammonia

2022 ◽  
Author(s):  
Zhen Feng ◽  
Zelin Yang ◽  
Xiaowen Meng ◽  
Fachuang Li ◽  
Zhanyong Guo ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Metal Organic Frameworks ◽  
Density Functional Theory Calculations ◽  
Reduction Reaction ◽  
Single Atom ◽  
Two Dimensional ◽  
Functional Theory ◽  
New Family ◽  
Metal Organic

The development of single-atom catalysts (SACs) for electrocatalytic nitrogen reduction reaction (NRR) remains a great challenge. Using density functional theory calculations, we design a new family of two-dimensional metal-organic frameworks...

scholarly journals Influence of Varying Functionalization on the Peroxidase Activity of Nickel(II)–Pyridine Macrocycle Catalysts: Mechanistic Insights from Density Functional Theory

Computation ◽  
2020 ◽  
Vol 8 (2) ◽  
pp. 52
Author(s):  
Jerwin Jay E. Taping ◽  
Junie B. Billones ◽  
Voltaire G. Organo
Keyword(s):  
Density Functional Theory ◽  
Proton Transfer ◽  
Density Functional ◽  
Experimental Studies ◽  
Density Functional Theory Calculations ◽  
Catalytic Performance ◽  
Stoichiometric Ratio ◽  
Functional Theory ◽  
Pendant Arm ◽  
Spin Singlet

Nickel(II) complexes of mono-functionalized pyridine-tetraazamacrocycles (PyMACs) are a new class of catalysts that possess promising activity similar to biological peroxidases. Experimental studies with ABTS (2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid), substrate) and H2O2 (oxidant) proposed that hydrogen-bonding and proton-transfer reactions facilitated by their pendant arm were responsible for their catalytic activity. In this work, density functional theory calculations were performed to unravel the influence of pendant arm functionalization on the catalytic performance of Ni(II)–PyMACs. Generated frontier orbitals suggested that Ni(II)–PyMACs activate H2O2 by satisfying two requirements: (1) the deprotonation of H2O2 to form the highly nucleophilic HOO−, and (2) the generation of low-spin, singlet state Ni(II)–PyMACs to allow the binding of HOO−. COSMO solvation-based energies revealed that the O–O Ni(II)–hydroperoxo bond, regardless of pendant arm type, ruptures favorably via heterolysis to produce high-spin (S = 1) [(L)Ni3+–O·]2+ and HO−. Aqueous solvation was found crucial in the stabilization of charged species, thereby favoring the heterolytic process over homolytic. The redox reaction of [(L)Ni3+–O·]2+ with ABTS obeyed a 1:2 stoichiometric ratio, followed by proton transfer to produce the final intermediate. The regeneration of Ni(II)–PyMACs at the final step involved the liberation of HO−, which was highly favorable when protons were readily available or when the pKa of the pendant arm was low.

scholarly journals High-Throughput Screening Single-Atom Alloy for Electroreduction of Dinitrogen to Ammonia

2021 ◽  
Author(s):  
Guokui Zheng ◽  
Ziqi Tian ◽  
Xingwang Zhang ◽  
Liang Chen ◽  
Xu Qian ◽  
...  
Keyword(s):  
High Throughput Screening ◽  
Density Functional ◽  
Ammonia Synthesis ◽  
Density Functional Theory Calculations ◽  
Reduction Reaction ◽  
Single Atom ◽  
Functional Theory ◽  
Metal Doped ◽  
Single Atom Alloy ◽  
Single Atom Alloys

<p></p><p>Exploring electrocatalyst with high activity, selectivity and stability is essential for development of applicable electrocatalytic ammonia synthesis technology. By performing density functional theory calculations, we systematically investigated a series of transition-metal doped Au-based single atom alloys (SAAs) as promising electrocatalysts for nitrogen reduction reaction (NRR). For Au-based electrocatalyst, the first hydrogenation step (*N<sub>2</sub>→*NNH) normally determines the limiting potential of the overall reaction process. Compared with pristine Au(111) surface, introducing single atom can significantly enhance the binding strength of N<sub>2</sub>, leading to decreased energy barrier of the key step, i.e., ΔG(*N<sub>2</sub>→*NNH). According to simulation results, three descriptors were proposed to describe ΔG(*N<sub>2</sub>→*NNH), including ΔG(*NNH), <i>d</i>-band center, and . Eight doped elements (Ti, V, Nb, Ru, Ta, Os, W, and Mo) were initially screened out with limiting potential ranging from -0.75V to -0.30 V. Particularly, Mo- and W-doped systems possess the best activity with limiting potentials of -0.30 V, respectively. Then the intrinsic relationship between structure and the potential performance was further analyzed by using machine-learning. The selectivity, feasibility, stability of these candidates were also evaluated, confirming that SAA containing Mo, Ru ,Ta, and W could be outstanding NRR electrocatalysts. This work not only broadens the understating of SAA application in electrocatalysis, but also devotes to the discovery of novel NRR electrocatalysts.</p><br><p></p>

scholarly journals Transition Metal Oxynitrides Catalysts for Electrochemical Reduction of Nitrogen to Ammonia

2021 ◽  
Author(s):  
Damilola Ologunagba ◽  
Shyam Kattel
Keyword(s):  
Density Functional Theory ◽  
Transition Metal ◽  
Dft Calculations ◽  
Electrochemical Reduction ◽  
Density Functional ◽  
Reduction Reaction ◽  
Ambient Conditions ◽  
Functional Theory ◽  
Nitrogen Reduction ◽  
Bosch Process

Electrochemical nitrogen reduction reaction (ENRR) at ambient conditions is beneficial compared to energy intensive thermochemical Haber-Bosch process for NH3 production. Here, periodic density functional theory (DFT) calculations are carried out...

scholarly journals Single-atom Sn-Zn pairs in CuO catalyst promote dimethyldichlorosilane synthesis

2019 ◽  
Vol 7 (3) ◽  
pp. 600-608 ◽  
Author(s):  
Qi Shi ◽  
Yongjun Ji ◽  
Wenxin Chen ◽  
Yongxia Zhu ◽  
Jing Li ◽  
...  
Keyword(s):  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Catalytic Performance ◽  
Utilization Efficiency ◽  
Single Atom ◽  
Electronic Interaction ◽  
Active Components ◽  
Functional Theory ◽  
Low Concentrations ◽  
Sn Substitution

Abstract Single-atom catalysts are of great interest because they can maximize the atom-utilization efficiency and generate unique catalytic properties; however, much attention has been paid to single-site active components, rarely to catalyst promoters. Promoters can significantly affect the activity and selectivity of a catalyst, even at their low concentrations in catalysts. In this work, we designed and synthesized CuO catalysts with atomically dispersed co-promoters of Sn and Zn. When used as the catalyst in the Rochow reaction for the synthesis of dimethyldichlorosilane, this catalyst exhibited much-enhanced activity, selectivity and stability compared with the conventional CuO catalysts with promoters in the form of nanoparticles. Density functional theory calculations demonstrate that single-atomic Sn substitution in the CuO surface can enrich surface Cu vacancies and promote dispersion of Zn to its atomic levels. Sn and Zn single sites as the co-promoters cooperatively generate electronic interaction with the CuO support, which further facilitates the adsorption of the reactant molecules on the surface, thereby leading to the superior catalytic performance.

Bifunctional Electrocatalyst for Oxygen Reduction and Oxygen Evolution: Theoretical Study on 2D Metallic WO2-supported Single Atom (Fe, Co, Ni) Catalysts

2021 ◽  
Author(s):  
Yuli Ma ◽  
Fangming Jin ◽  
Yun Hang Hu
Keyword(s):  
Oxygen Reduction ◽  
Oxygen Evolution ◽  
Density Functional ◽  
Critical Role ◽  
Reduction Reaction ◽  
Single Atom ◽  
Ni Catalysts ◽  
Functional Theory ◽  
Bifunctional Electrocatalyst ◽  
Principle Density Functional Theory

Catalysts play a critical role in oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) for energy storage, conversion, and utilization. Herein, first-principle density functional theory (DFT) calculations demonstrated that...

CO oxidation over the polyoxometalate-supported single-atom catalysts M1/POM (Fe, Co, Mn, Ru, Rh, Os, Ir, and Pt; POM = [PW12O40]3–): a computational study on the activation of surface oxygen species

2019 ◽  
Vol 48 (18) ◽  
pp. 6228-6235 ◽  
Author(s):  
Chun-Guang Liu ◽  
Li-Long Zhang ◽  
Xue-Mei Chen
Keyword(s):  
Density Functional Theory ◽  
Co Oxidation ◽  
Density Functional ◽  
Computational Study ◽  
Density Functional Theory Calculations ◽  
Catalytic Performance ◽  
Single Atom ◽  
Oxygen Species ◽  
Surface Oxygen ◽  
Functional Theory

Density functional theory calculations have been carried out to explore the catalytic performance of a series of the M1/POM (M = Fe, Co, Mn, Ru, Rh, Os, Ir, and Pt; POM = [PW12O40]3−) single-atom catalysts for CO oxidation.

scholarly journals Noble metal supported hexagonal boron nitride for the oxygen reduction reaction: a DFT study

2019 ◽  
Vol 1 (1) ◽  
pp. 132-139 ◽  
Author(s):  
Seoin Back ◽  
Samira Siahrostami
Keyword(s):  
Boron Nitride ◽  
Oxygen Reduction Reaction ◽  
Oxygen Reduction ◽  
Density Functional ◽  
Hexagonal Boron Nitride ◽  
Density Functional Theory Calculations ◽  
Cost Effective ◽  
Reduction Reaction ◽  
Functional Theory ◽  
The Stability

Discovering active, stable and cost-effective catalysts for the oxygen reduction reaction (ORR) is of utmost interest for commercialization of fuel cells. Herein, we use density functional theory calculations to systematically study metal supported hexagonal boron nitride as ORR catalysts. Our results indicate that this strategy is a promising to increase the stability against CO poisoning as well as to activate inert h-BN toward the ORR.

scholarly journals Quantum Simulation of the Silicene and Germanene for Sensing and Sequencing of DNA/RNA Nucleobases

Biosensors ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 59
Author(s):  
Hikmet Hakan Gürel ◽  
Bahadır Salmankurt
Keyword(s):  
Density Functional ◽  
2D Materials ◽  
High Surface ◽  
Experimental Studies ◽  
Interaction Mechanism ◽  
Volume Ratio ◽  
First Principle ◽  
Functional Theory ◽  
Silicon And Germanium ◽  
Insight Into

Over the last decade, we have been witnessing the rise of two-dimensional (2D) materials. Several 2D materials with outstanding properties have been theoretically predicted and experimentally synthesized. 2D materials are good candidates for sensing and detecting various biomolecules because of their extraordinary properties, such as a high surface-to-volume ratio. Silicene and germanene are the monolayer honeycomb structures of silicon and germanium, respectively. Quantum simulations have been very effective in understanding the interaction mechanism of 2D materials and biomolecules and may play an important role in the development of effective and reliable biosensors. This article focuses on understanding the interaction of DNA/RNA nucleobases with silicene and germanane monolayers and obtaining the possibility of using silicene and germanane monolayers as a biosensor for DNA/RNA nucleobases’ sequencing using the first principle of Density Functional Theory (DFT) calculations with van der Waals (vdW) correction and nonequilibrium Green’s function method. Guanine (G), Cytosine (C), Adenine (A), Thymine (T), and Uracil (U) were examined as the analytes. The strength of adsorption between the DNA/RNA nucleobases and silicene and germanane is G > C > A > T > U. Moreover, our recent work on the investigation of Au- and Li-decorated silicene and germanane for detection of DNA/RNA nucleobases is presented. Our results show that it is possible to get remarkable changes in transmittance due to the adsorption of nucleobases, especially for G, A, and C. These results indicate that silicene and germanene are both good candidates for the applications in fast sequencing devices for DNA/RNA nucleobases. Additionally, our present results have the potential to give insight into experimental studies and can be valuable for advancements in biosensing and nanobiotechnology.

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