10th Anniversary of Catalysts: Achievements in Computational Catalysis Techniques and Applications

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

Deadline for manuscript submissions: closed (31 December 2021) | Viewed by 10730

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Department of Chemical and Biological Engineering, The University of Alabama, Box 870203, Tuscaloosa, AL 35487, USA
Interests: computational catalysis; DFT calculations; kinetic Monte Carlo simulations; electrocatalysis; adsorption; porous materials; interfacial catalysis; nanoparticle synthesis; polymeric membranes; separations
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Guest Editor
Department of Chemical and Biological Engineering, The University of Alabama, Box 870203, Tuscaloosa, Alabama 35487, USA
Interests: computational catalysis; electronic structure calculations; molecular simulations; liquid crystals; interfacial phenomena; materials for energy applications

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Guest Editor
College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Songjiang District, Shanghai 201620, China
Interests: computational catalysis; electrocatalysis; biooils upgrading reactions; CO2 reduction reaction; oxygen reduction reaction; DFT calculations

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Guest Editor
School of Chemistry, Xi’an Jiaotong University, Xi’an, China
Interests: computational chemistry; density functional theory; molecular dynamics simulation; machine learning; heterogeneous catalysis; energy catalytic materials; single-atom catalysis

Special Issue Information

Dear Colleagues,

 In 2021, Catalysts will reach a significant milestone in its history by welcoming its tenth anniversary. In order to celebrate this special occasion, we will be launching a Special Issue in the Computational Catalysis subsection entitled “10th Anniversary of Catalysts: Achievements in Computational Catalysis Techniques and Applications.” We will be editing a Special Issue of comprehensive reviews and particularly impactful original articles. Computational catalysis has emerged as one of the fastest growing research fields in the last decade, and it now represents a critical tool for the analysis of chemical mechanisms and active sites. As the field of computational catalysis continues to expand, the gap between models and reality is beginning to narrow. We are particularly interested in articles that investigate the secondary effects influencing catalysis and reaction mechanisms. This includes the role of structural defects, the solvation environment or neighbor-neighbor effects, deactivation events, and work that incorporates system features encountered at finite temperatures. Furthermore, we are interested in new techniques and applications that enable extended time scale analyses, as well as high throughput screening techniques that involve machine learning or descriptor-based protocols.

We would like to thank all our Editorial Board Members, Editors, Reviewers, and Authors for their great contributions and continuous support over the last decade. Please help us to celebrate our 10th Anniversary and participate by submitting your work to this Special Issue.

Prof. Dr. C. Heath Turner
Prof. Dr. Tibor Szilvási
Prof. Dr. Wei An
Prof. Dr. Yaqiong Su
Guest Editors

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Keywords

  • Ab initio
  • Density-functional theory
  • Reaction mechanism
  • Computations
  • Modeling
  • Kinetic Monte Carlo
  • Machine learning
  • Deactivation
  • Electrocatalysis
  • Screening

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Published Papers (4 papers)

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Research

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26 pages, 5901 KiB  
Article
BF3–Catalyzed Diels–Alder Reaction between Butadiene and Methyl Acrylate in Aqueous Solution—An URVA and Local Vibrational Mode Study
by Marek Freindorf and Elfi Kraka
Catalysts 2022, 12(4), 415; https://doi.org/10.3390/catal12040415 - 7 Apr 2022
Cited by 4 | Viewed by 2254
Abstract
In this study we investigate the Diels–Alder reaction between methyl acrylate and butadiene, which is catalyzed by BF3 Lewis acid in explicit water solution, using URVA and Local Mode Analysis as major tools complemented with NBO, electron density and ring puckering analyses. [...] Read more.
In this study we investigate the Diels–Alder reaction between methyl acrylate and butadiene, which is catalyzed by BF3 Lewis acid in explicit water solution, using URVA and Local Mode Analysis as major tools complemented with NBO, electron density and ring puckering analyses. We considered four different starting orientations of methyl acrylate and butadiene, which led to 16 DA reactions in total. In order to isolate the catalytic effects of the BF3 catalyst and those of the water environment and exploring how these effects are synchronized, we systematically compared the non-catalyzed reaction in gas phase and aqueous solution with the catalyzed reaction in gas phase and aqueous solution. Gas phase studies were performed at the B3LYP/6-311+G(2d,p) level of theory and studies in aqueous solution were performed utilizing a QM/MM approach at the B3LYP/6-311+G(2d,p)/AMBER level of theory. The URVA results revealed reaction path curvature profiles with an overall similar pattern for all 16 reactions showing the same sequence of CC single bond formation for all of them. In contrast to the parent DA reaction with symmetric substrates causing a synchronous bond formation process, here, first the new CC single bond on the CH2 side of methyl acrylate is formed followed by the CC bond at the ester side. As for the parent DA reaction, both bond formation events occur after the TS, i.e., they do not contribute to the energy barrier. What determines the barrier is the preparation process for CC bond formation, including the approach diene and dienophile, CC bond length changes and, in particular, rehybridization of the carbon atoms involved in the formation of the cyclohexene ring. This process is modified by both the BF3 catalyst and the water environment, where both work in a hand-in-hand fashion leading to the lowest energy barrier of 9.06 kcal/mol found for the catalyzed reaction R1 in aqueous solution compared to the highest energy barrier of 20.68 kcal/mol found for the non-catalyzed reaction R1 in the gas phase. The major effect of the BF3 catalyst is the increased mutual polarization and the increased charge transfer between methyl acrylate and butadiene, facilitating the approach of diene and dienophile and the pyramidalization of the CC atoms involved in the ring formation, which leads to a lowering of the activation energy. The catalytic effect of water solution is threefold. The polar environment leads also to increased polarization and charge transfer between the reacting species, similar as in the case of the BF3 catalyst, although to a smaller extend. More important is the formation of hydrogen bonds with the reaction complex, which are stronger for the TS than for the reactant, thus stabilizing the TS which leads to a further reduction of the activation energy. As shown by the ring puckering analysis, the third effect of water is space confinement of the reacting partners, conserving the boat form of the six-member ring from the entrance to the exit reaction channel. In summary, URVA combined with LMA has led to a clearer picture on how both BF3 catalyst and aqueous environment in a synchronized effort lower the reaction barrier. These new insights will serve to further fine-tune the DA reaction of methyl acrylate and butadiene and DA reactions in general. Full article
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12 pages, 4689 KiB  
Article
Cu/O Frustrated Lewis Pairs on Cu Doped CeO2(111) for Acetylene Hydrogenation: A First-Principles Study
by Shulan Zhou, Qiang Wan and Sen Lin
Catalysts 2022, 12(1), 74; https://doi.org/10.3390/catal12010074 - 10 Jan 2022
Cited by 11 | Viewed by 2610
Abstract
In this work, the H2 dissociation and acetylene hydrogenation on Cu doped CeO2(111) were studied using density functional theory calculations. The results indicated that Cu doping promotes the formation of oxygen vacancy (Ov) which creates Cu/O and Ce/O [...] Read more.
In this work, the H2 dissociation and acetylene hydrogenation on Cu doped CeO2(111) were studied using density functional theory calculations. The results indicated that Cu doping promotes the formation of oxygen vacancy (Ov) which creates Cu/O and Ce/O frustrated Lewis pairs (FLPs). With the help of Cu/O FLP, H2 dissociation can firstly proceed via a heterolytic mechanism to produce Cu-H and O-H by overcoming a barrier of 0.40 eV. The H on Cu can facilely migrate to a nearby oxygen to form another O-H species with a barrier of 0.43 eV. The rate-determining barrier is lower than that for homolytic dissociation of H2 which produces two O-H species. C2H2 hydrogenation can proceed with a rate-determining barrier of 1.00 eV at the presence of Cu-H and O-H species., While C2H2 can be catalyzed by two O-H groups with a rate-determining barrier of 1.06 eV, which is significantly lower than that (2.86 eV) of C2H2 hydrogenated by O-H groups on the bare CeO2(111), showing the high activity of Cu doped CeO2(111) for acetylene hydrogenation. In addition, the rate-determining barrier of C2H4 further hydrogenated by two O-H groups is 1.53 eV, much higher than its desorption energy (0.72 eV), suggesting the high selectivity of Cu doped CeO2(111) for C2H2 partial hydrogenation. This provides new insights to develop effective hydrogenation catalysts based on metal oxide. Full article
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12 pages, 2185 KiB  
Article
Catalytic Performance of Cycloalkyl-Fused Aryliminopyridyl Nickel Complexes toward Ethylene Polymerization by QSPR Modeling
by Md Mostakim Meraz, Arfa Abrar Malik, Wenhong Yang and Wen-Hua Sun
Catalysts 2021, 11(8), 920; https://doi.org/10.3390/catal11080920 - 29 Jul 2021
Cited by 3 | Viewed by 2620
Abstract
Quantitative structure–property relationship (QSPR) modeling is performed to investigate the role of cycloalkyl-fused rings on the catalytic performance of 46 aryliminopyridyl nickel precatalysts. The catalytic activities for nickel complexes in ethylene polymerization are well-predicted by the obtained 2D-QSPR model, exploring the main contribution [...] Read more.
Quantitative structure–property relationship (QSPR) modeling is performed to investigate the role of cycloalkyl-fused rings on the catalytic performance of 46 aryliminopyridyl nickel precatalysts. The catalytic activities for nickel complexes in ethylene polymerization are well-predicted by the obtained 2D-QSPR model, exploring the main contribution from the charge distribution of negatively charged atoms. Comparatively, 3D-QSPR models show better predictive and validation capabilities than that of 2D-QSPR for both catalytic activity (Act.) and the molecular weight of the product (Mw). Three-dimensional contour maps illustrate the predominant effect of a steric field on both catalytic properties; smaller sizes of cycloalkyl-fused rings are favorable to Act.y, whereas they are unfavorable to Mw. This study may provide assistance in the design of a new nickel complex with high catalytic performance. Full article
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Review

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14 pages, 2764 KiB  
Review
High-Performance Ligand-Protected Metal Nanocluster Catalysts for CO2 Conversion through the Exposure of Undercoordinated Sites
by Dominic Alfonso
Catalysts 2022, 12(5), 505; https://doi.org/10.3390/catal12050505 - 30 Apr 2022
Cited by 6 | Viewed by 2004
Abstract
Previous experimental breakthroughs reveal the potential to create novel heterogeneous catalysts for the electroreduction of CO2 to a high-value product CO using ligand-protected Au-based nanoclusters. Since the chemical composition and geometric structures have been precisely defined, it is possible to adopt robust [...] Read more.
Previous experimental breakthroughs reveal the potential to create novel heterogeneous catalysts for the electroreduction of CO2 to a high-value product CO using ligand-protected Au-based nanoclusters. Since the chemical composition and geometric structures have been precisely defined, it is possible to adopt robust design guidelines for the development of practical catalysts and to fundamentally elucidate the underlying reaction mechanism. In this short review, the computational progress made to understand the experimentally observed reduction process on the following subset of materials—Au25(SR)18, Au24Pd(SR)18, Au23(SR)16 and Au21Cd2(SR)16—is described. A significant finding from our first-principles mechanistic studies is that CO2 conversion on the fully ligand protected nanoclusters is thermodynamically unfavorable due to the very weak binding of intermediates on the surface region. However, the reaction becomes feasible when either Au or S sites are exposed through the removal of a ligand. The results particularly point to the role of undercoordinated S sites in the creation of highly functional heterogeneous catalysts that are both active and selective for the CO2 conversion process. The incorporation of dopants could significantly influence the catalytic reactivity of the nanoclusters. As demonstrated in the case of the monopalladium substitution in Au25(SR)18, the presence of the foreign atom leads to an enhancement of CO production selectivity due to the greater stabilization of the intermediates. With the Cd substitution doping of Au23(SR)16, the improvement in performance is also attributed to the enhanced binding strength of the intermediates on the geometrically modified surface of the nanocluster. Full article
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