Recent advances in computational studies of organometallic sheets: Magnetism, adsorption and catalysis

Zhu, Guizhi; Sun, Qiang

doi:10.1016/j.commatsci.2015.07.020

Cited by 30 publications

(15 citation statements)

References 101 publications

(104 reference statements)

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“…[15] Similar to the TM-macrocyclic compounds, another series of two dimensional transition metal-organic structures, namely, TM-tetracyanoquinodimethane (TM-TCNQ) have gained immense research attention in recent past for its unique photoelectrical, photochemical, catalytic and magnetic properties. [16][17][18][19][20] Scholarly articles about various TM-TCNQ framework, mostly explored for oxygen reduction reaction (ORR), revealed that Fe-TCNQ is the best candidate for ORR electrocatalyst. [20,21] However, there has been no in-depth reports so far for TM-TCNQ based OER catalyst with detail investigations for density of states calculation and the corresponding free energy profile.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Electrocatalyst for Oxygen Evolution Reaction: DFT Investigation on Transition Metal‐Tetracyanoquinodimethane Monolayer

Mukherjee

2021

ChemistrySelect

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To search for efficient electrocatalyst towards oxygen evolution reaction (OER) for sustainable energy production, a family of transition metal-tetracyanoquinodimethane (TM-TCNQ) (TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd)monolayers have been studied by first principle based density functional theory (DFT) computations. The systematic investigations on various TM-TCNQ structures revealed that Ni-TCNQ monolayer exhibits best catalytic activity towards OER. At equilibrium potential (1.23 Vvs RHE), the free energy profile of Ni-TCNQ monolayer for different reaction intermediates is not completely downhill which points out that water could not be oxidized by the photo-generated holes at that potential. However, at and above 1.71 V, all the OER reaction steps on Ni-TCNQ surface is found to be thermodynamically downhill, measuring a low onset overpotential, ca. 0.48 V in acidic media (pH = 0). The estimated overpotential for other TM-TCNQ structures are comparatively higher to promote energy-efficient OER activity. The excellent performance of Ni-TCNQ monolayer as OER catalyst were explained in terms of volcano plot, scaling diagram, d-band centre model, band structure and charge analysis.

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Section: Introductionmentioning

confidence: 99%

Highly Efficient Electrocatalyst for Oxygen Evolution Reaction: DFT Investigation on Transition Metal‐Tetracyanoquinodimethane Monolayer

Mukherjee

2021

ChemistrySelect

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“…Especially, the successful synthesis of TM-PC [33][34][35] as a member of 2D COFs has attracted significant interest in its catalytic performance. For instance, the mechanism of NO adsorption on the surface of the TM-PCs (TM=Mn, Fe, Co) was studied [36,37], and their strong chemical adsorption was found to depend on the d electron state of the TM atoms; the Fe-PCs sheet was found to exhibit excellent catalytic performance for the oxygen reduction reaction [38]. Although there have been many reports of the TM-PCs in terms of catalytic reactions, the microcosmic mechanism studies of 2D TM-PCs towards NO degradation remain in their infancy.…”

Section: Introductionmentioning

confidence: 99%

Reduction Mechanism of NO Gas on Iron–Phthalocyanines (Fe–PCs): A DFT Investigation

Liu

2021

Catal Lett

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Achieving the removal of the toxic nitric oxide (NO) gas efficiently and cheaply has always been a challenge. Herein, we systematically investigate the reduction mechanisms of NO on the surface of the Fe-PCs (PCs = phthalocyanines) using density functional theory calculations. The isolated iron atom not only plays the role of an adsorption and activation site for the NO molecule but also works as an electron transfer medium in the whole reaction process. The results indicate that the catalytic reduction of NO to N 2 takes place through a continuous two-step pathway. The first step involves the reduction of NO to N 2 O through a competitive Langmuir-Hinshelwood and Eley-Rideal mechanisms with the energy barrier of 1.19 eV and 0.60 eV, respectively. The second step involves the reduction of N 2 O to N 2 with an energy barrier of 0.91 eV. These reaction pathways are favorable thermodynamically, thus the Fe-PCs catalyst is a promising candidate for the abatement of NO gases.

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“…Another family of 2-D transition metal-organic molecules, viz, TMtetracyanoquinodimethane (TM-TCNQ), which is similar to the TM-macrocyclic structure, have been explored recently by different groups due to their promising photoelectrochemical and catalytic properties [22][23][24][25][26][27]. However, the span of diverse activities and the potential of these TM-TCNQ composition till remains unexplored, especially their possible extent as both ORR and OER (bi-functional) electrocatalyst is largely unknown [26].…”

Section: Introductionmentioning

confidence: 99%

Cobalt−Tetracyanoquinodimethane Monolayer as Efficient Bi-Functional Single Atom Electrocatalyst: A First Principles Investigation

Mukherjee

2021

Preprint

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A bi-functional electrocatalyst is a stable and catalytically active material for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), the development of which is highly challenging, although essential for application in fuel cells. Herein, the first principle based density functional theory (DFT) computations have been carried out to investigate a series of transition metal-tetracyanoquinodimethane (TM-TCNQ: TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd) monolayer for bi-functional single atom electrocatalyst towards ORR and OER. Amongst various first transition metal row based TCNQ substrates, Cobalt-TCNQ (Co-TCNQ) monolayer was predicted to exhibit best bi-functional catalytic activity. At equilibrium potential (1.23 V, vs RHE), the free energy portraits of Co-TCNQ monolayer for OER in acidic or alkaline media are not completely downhill, measuring an excess potential of 0.6 V, equal to the overpotential, which is needed to be supplied externally to promote the OER activity. On the other hand, an onset potentials of 0.34 V (vs RHE) in acidic media are measured for ORR to proceed. The promising catalytic activity of two dimensional Co-TCNQ monolayer towards ORR and OER as revealed by DFT investigations has been explained in terms of density of states and Bader charge analysis.

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Recent advances in computational studies of organometallic sheets: Magnetism, adsorption and catalysis

Cited by 30 publications

References 101 publications

Highly Efficient Electrocatalyst for Oxygen Evolution Reaction: DFT Investigation on Transition Metal‐Tetracyanoquinodimethane Monolayer

Highly Efficient Electrocatalyst for Oxygen Evolution Reaction: DFT Investigation on Transition Metal‐Tetracyanoquinodimethane Monolayer

Reduction Mechanism of NO Gas on Iron–Phthalocyanines (Fe–PCs): A DFT Investigation

Cobalt−Tetracyanoquinodimethane Monolayer as Efficient Bi-Functional Single Atom Electrocatalyst: A First Principles Investigation

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