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Catalysts
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Computational Insights into Small Molecule Activation
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Computational Insights into Small Molecule Activation

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Computational Catalysis".

Deadline for manuscript submissions: closed (1 March 2023) | Viewed by 7593

Special Issue Editors

Dr. Guangchao Liang

E-Mail Website
Guest Editor
Academy of Advanced Interdisciplinary Research, Xidian University, Xi’an 710071, China
Interests: catalysis and mechanism; computational chemistry; inorganic and organometallic chemistry
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Charles Edwin Webster

E-Mail Website
Guest Editor
Department of Chemistry, Mississippi State University, Mississippi State, MS 39762, USA
Interests: theoretical and computational catalysis; homogeneous catalysis; inorganic and bioinorganic; kinetics and mechanisms
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Over the past decades, chemists have dedicated great efforts to promoting the activation of small molecules (such as H2O, H2, N2, O2, CO2, N2O, H2O2, CH4, and other C2/C3 organic compounds) to pursue high-value chemical feedstocks and to obtain new energy resources. Chemical catalysis, electrocatalysis and photocatalysis performed with inorganic and organometallic complexes have demonstrated their superior merits in the activation of small molecules, and computational investigations have strengthened their advantages by providing significant and fundamental understanding. Grand challenges still exist in breaking the strong chemical bonds of small molecules, which limit the practical implementation of the catalytic system. Interpretation of experimental observations, understanding of reaction mechanisms, identification of active species, explanation of the deactivation of catalysts, and the design of catalysts have been promoted by computational approaches. Studies from density functional theory, ab initio modeling, data science, and artificial intelligence have been demonstrated as the non-negligible components to establish the novel catalytic systems for the activation of small molecules.

This Special Issue “Computational Insights into Small Molecule Activation” covers, but is not limited to, high-quality research papers and review articles that report the advances, developments, and challenges in the activation of small molecules, and especially the computational interpretations of catalytic mechanisms and the reasonable design of catalysts. Both homogeneous and heterogeneous catalysis with inorganic and organometallic complexes are welcome.

Dr. Guangchao Liang
Prof. Dr. Charles Edwin Webster
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • computational catalysis
  • small molecule activation
  • catalyst design
  • structure-functional analysis
  • homogeneous catalysis
  • heterogeneous catalysis

Published Papers (5 papers)

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Research

11 pages, 2146 KiB  
Article
Correlation between Key Steps and Hydricity in CO2 Hydrogenation Catalysed by Non-Noble Metal PNP-Pincer Complexes
by Snehasis Moni and Bhaskar Mondal
Catalysts 2023, 13(3), 592; https://doi.org/10.3390/catal13030592 - 15 Mar 2023
Cited by 4 | Viewed by 1562
Abstract
Transition metal-catalysed homogeneous hydrogenation of CO2 to formate or formic acid has emerged as an appealing strategy for the reduction of CO2 into value-added chemicals. Since the state-of-the-art catalysts in this realm are primarily based on expensive precious metals and require [...] Read more.
Transition metal-catalysed homogeneous hydrogenation of CO2 to formate or formic acid has emerged as an appealing strategy for the reduction of CO2 into value-added chemicals. Since the state-of-the-art catalysts in this realm are primarily based on expensive precious metals and require demanding reaction conditions, the design and development of economically viable non-noble metal catalysts are in great demand. Herein, we exploit the thermodynamic correlation between the crucial reaction steps of CO2 hydrogenation, that is, base-promoted H2-splitting and hydride transfer to CO2 as a guide to estimate the catalytic efficiency of non-noble metal complexes possessing a ligand backbone containing a secondary amine as an “internal base”. A set of three non-noble metal complexes, one bearing tri-coordinated PNP-pincer (1Mn) and the other two based on tetra-coordinated PNPN-pincer (2Mn and 3Fe), have been investigated in this study. The computational mechanistic investigation establishes the role of the “internal” amine base in heterolytically splitting the metal-bound H2, a critical step for CO2 hydrogenation. Furthermore, the thermodynamic correlation between the hydricity (ΔGH−°) of the in situ generated metal-hydride species and the free energy barrier of the two crucial steps could provide an optimal hydricity value for efficient catalytic activity. Based on the computational estimation of the optimal hydricity value, the tri-coordinated PNP-pincer complex 1Mn appears to be the most efficient among the three, with the other two tetra-coordinated PNPN-pincer complexes, 2Mn and 3Fe, showing promising hydricity values. Overall, this study demonstrates how the crucial thermodynamic and kinetic parameters for pincer-based complexes possessing an “internal base” can be correlated for the prediction of novel non-noble metal-based catalysts for CO2 hydrogenation. Full article
(This article belongs to the Special Issue Computational Insights into Small Molecule Activation)
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12 pages, 4375 KiB  
Article
Theoretically Predicted CO Adsorption and Activation on the Co-Doped hcp-Fe7C3 Catalyst
by Yajing Duan, Huijuan Sun, Hui Du and Wencai Lu
Catalysts 2023, 13(3), 564; https://doi.org/10.3390/catal13030564 - 11 Mar 2023
Cited by 1 | Viewed by 1011
Abstract
The Hcp-Fe7C3 phase has attracted more attention due to the high catalytic activity in Fischer–Tropsch synthesis (FTS) reactions. In this work, the adsorption and activation of CO on a Co-doped hcp-Fe7C3 catalyst were investigated by density functional [...] Read more.
The Hcp-Fe7C3 phase has attracted more attention due to the high catalytic activity in Fischer–Tropsch synthesis (FTS) reactions. In this work, the adsorption and activation of CO on a Co-doped hcp-Fe7C3 catalyst were investigated by density functional theory (DFT) in order to understand the effect of Co doping on the initial step of FTS reactions on iron-based catalysts. Different Co-doped hcp-Fe7C3 001 and 11¯0 surfaces were constructed, and the CO adsorption configurations were studied. The calculated results show that the structure of the 001 surface remains basically unchanged after doping with Co atoms, while the replacement of Fe or C atoms on 11¯0 surfaces with Co atoms has a significant impact on the surface structure. The top sites on the doped Co atoms of hcp-Fe7C3 are disadvantages for the CO adsorption, whereas the T, 2F, or 3F sites around the doped Co atoms are beneficial for promoting the adsorption of CO. The CO direct dissociation pathways on the four types of Co-doped hcp-Fe7C3 001 surfaces are exothermic, while the H-assisted dissociation pathways of CO are endothermic. The H-assisted activation via HCO on the 3F1 site of the 2Co2-doped hcp-Fe7C3 001 surface shows the lowest energy barrier of 1.96 eV. For the Co-doped hcp-Fe7C3 11¯0 surfaces, the H-assisted activation via HCO is the preferred activation pathway for CO on the Co-doped surfaces with the energy barrier of approximately 1.30 eV. Full article
(This article belongs to the Special Issue Computational Insights into Small Molecule Activation)
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7 pages, 2944 KiB  
Communication
The C-H Bond Activation Triggered by Subsurface Mo Dopant on MgO Catalyst in Oxidative Coupling of Methane
by Xiaoying Sun, Xinyu Li, Yue Liu, Zhan Yu, Bo Li and Zhen Zhao
Catalysts 2022, 12(10), 1083; https://doi.org/10.3390/catal12101083 - 20 Sep 2022
Cited by 1 | Viewed by 1129
Abstract
In this work, density functional theory calculations are performed to explore the unique role of Mo dopant on MgO in oxidative coupling of methane. It is revealed that subsurface Mo dopant significantly enhanced the adsorption and activation of oxygen molecules. The combination of [...] Read more.
In this work, density functional theory calculations are performed to explore the unique role of Mo dopant on MgO in oxidative coupling of methane. It is revealed that subsurface Mo dopant significantly enhanced the adsorption and activation of oxygen molecules. The combination of adsorbed oxygen and surface Mg exhibited a balanced activity for C-H bond activation and release of methyl radical which paves the way to activate methane with a promising yield. Full article
(This article belongs to the Special Issue Computational Insights into Small Molecule Activation)
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7 pages, 1523 KiB  
Communication
Revealing the Synergetic Effects between Reactants in Oxidative Coupling of Methane on Stepped MgO(100) Catalyst
by Xiaoying Sun, Yue Liu, Xinyu Li, Zhan Yu, Bo Li and Zhen Zhao
Catalysts 2022, 12(8), 903; https://doi.org/10.3390/catal12080903 - 17 Aug 2022
Viewed by 1310
Abstract
The oxidative coupling of methane (OCM) on MgO is often computationally explored via Mars-Krevelen (MvK) mechanism. However, the difficult desorption of CH3 radical at stepped MgO surface shadow the feasibility of mechanism. In this work, density functional theory calculations are performed to [...] Read more.
The oxidative coupling of methane (OCM) on MgO is often computationally explored via Mars-Krevelen (MvK) mechanism. However, the difficult desorption of CH3 radical at stepped MgO surface shadow the feasibility of mechanism. In this work, density functional theory calculations are performed to unravel the syngenetic effects between reactants which lead to a new Langmuir-Hinshelwood (L-H)-like mechanism. It was found that co-adsorption of reactants pave ways for CH3 radical formation with negligible desorption energy. The role of oxygen molecule is not only to oxidize reduced surface but also decrease the reactivity of Mg-O site which facile CH3 desorption. Electronic structure analysis indicated the distinct feature along pathway between MvK and L-H. The current work clearly indicated the importance of effective interactions between reactants and provided new insights on the reaction mechanism of OCM. Full article
(This article belongs to the Special Issue Computational Insights into Small Molecule Activation)
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13 pages, 2794 KiB  
Article
Insights into the Capture of CO2 by Nickel Hydride Complexes
by Min Zhang, Xiaoqing Liang, Yaozheng Wang, Hongyu Yang and Guangchao Liang
Catalysts 2022, 12(7), 790; https://doi.org/10.3390/catal12070790 - 19 Jul 2022
Cited by 3 | Viewed by 1846
Abstract
As a desired feedstock for sustainable energy source and for chemical synthesis, the capture and utilization of CO2 have attracted chemists’ continuous efforts. The homogeneous CO2 insertion into a nickel hydride complex to generate formate provides insight into the role of [...] Read more.
As a desired feedstock for sustainable energy source and for chemical synthesis, the capture and utilization of CO2 have attracted chemists’ continuous efforts. The homogeneous CO2 insertion into a nickel hydride complex to generate formate provides insight into the role of hydrogen as an active hydride form in the hydrogenation of CO2, which serves as a practicable approach for CO2 utilization. To parameterize the activities and to model the structure–activity relationship in the CO2 insertion into nickel hydride, the comprehensive mechanism of CO2 insertion into a series of square planar transition metal hydride (TM–H, TM = Ni, Pd, and Co) complexes was investigated using density functional theory (DFT) computations. The stepwise pathway with the TM-(H)-formate intermediate for the CO2 insertion into all seven square planar transition metal hydride (TM–H) complexes was observed. The overall rate-determining step (RDS) was the nucleophilic attraction of the terminal O atom on the Ni center in Ni-(H)-formate to form Ni-(O)-(exo)formate. The charge of the Ni atom in the axially vacant [Ni]+ complex was demonstrated as the dominant factor in CO2 insertion, which had an excellent linear correction (R2 = 0.967) with the Gibbs barrier (ΔG‡) of the RDS. The parameterized activities and modeled structure–activity relationship provided here light the way to the design of a more efficient Ni–H complex in the capture and utilization of CO2. Full article
(This article belongs to the Special Issue Computational Insights into Small Molecule Activation)
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