Theory-Guided Electrocatalysis and Photocatalysis

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

Deadline for manuscript submissions: closed (15 November 2023) | Viewed by 10768

Special Issue Editors


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Guest Editor
School of Physical Science and Technology, Inner Mongolia University, Hohhot 010021, China
Interests: low-dimensional nanomaterial design and exploration of first principles
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Guest Editor
College of Chemistry and Chemical Engineering, Key Laboratory of Photonic and Electronic Bandgap Materials, Ministry of Education, Harbin Normal University, Harbin 150025, China
Interests: two-dimensional nanomaterials; catalytic performance
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The present Special Issue of Catalysts is aimed at presenting the recent development of theory-guided electrocatalysis and photocatalysis, and researchers working in the field are cordially invited to contribute.

Original articles dealing with electrocatalyzing and photocatalyzing CO2 reduction, N2 reduction, oxygen reduction/revolution, and hydrogen revolution reactions by means of theoretical computations are welcome.

Prof. Dr. Fengyu Li
Prof. Dr. Jingxiang Zhao
Guest Editors

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Keywords

  • electrocatalysis
  • photocatalysis
  • computations
  • efficiency
  • mechanism

Published Papers (7 papers)

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Research

14 pages, 4179 KiB  
Article
Noble Metal Single-Atom Coordinated to Nitrogen, Oxygen, and Carbon as Electrocatalysts for Oxygen Evolution
by Jianhua Wang, Jiangdong Bai, Yaqi Cang, Qing Li, Xing Fan and Haiping Lin
Catalysts 2023, 13(10), 1378; https://doi.org/10.3390/catal13101378 - 19 Oct 2023
Viewed by 1057
Abstract
Tuning the coordination environment centering metal atoms has been regarded as a promising strategy to promote the activities of noble metal single-atom catalysts (SACs). In the present work, first-principle calculations are employed to explore the oxygen evolution reaction (OER) performance of Ir and [...] Read more.
Tuning the coordination environment centering metal atoms has been regarded as a promising strategy to promote the activities of noble metal single-atom catalysts (SACs). In the present work, first-principle calculations are employed to explore the oxygen evolution reaction (OER) performance of Ir and Ru SACs with chemical coordination being nitrogen (M-N4-C), oxygen (M-O4-C), and carbon (M-C4-C) in graphene, respectively. A “three-step” strategy was implemented by progressively investigating these metrics (stability, catalytic activity, structure–activity relationship). A volcano plot of reactivity is established by using the adsorption-free energy of O* (∆GO*) as a theoretical descriptor. The intrinsic OER activity is IrN4-C > IrO4-C > RuO4-C > RuN4-C > IrC4-C > RuC4-C. The in-depth tuning mechanism of ∆GO* can be indicated and interpreted by the d-band centers of the active sites and the crystal orbital Hamilton population analysis of metal-oxygen bonds, respectively. Full article
(This article belongs to the Special Issue Theory-Guided Electrocatalysis and Photocatalysis)
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15 pages, 4043 KiB  
Article
Mechanism of Methanol Synthesis from CO2 Hydrogenation over Cu/γ-Al2O3 Interface: Influences of Surface Hydroxylation
by Hegen Zhou, Hua Jin, Yanli Li, Yi Li, Shuping Huang, Wei Lin, Wenkai Chen and Yongfan Zhang
Catalysts 2023, 13(9), 1244; https://doi.org/10.3390/catal13091244 - 27 Aug 2023
Cited by 1 | Viewed by 1145
Abstract
The adsorption and hydrogenation of carbon dioxide on γ-Al2O3(110) surface-supported copper clusters of different sizes are investigated using density functional theory calculations. Our results show that the activation of CO2 is most obvious at the Cu/γ-Al2O [...] Read more.
The adsorption and hydrogenation of carbon dioxide on γ-Al2O3(110) surface-supported copper clusters of different sizes are investigated using density functional theory calculations. Our results show that the activation of CO2 is most obvious at the Cu/γ-Al2O3 interface containing the size-selected Cu4 cluster. It is interesting that the CO2 activation is more pronounced at the partially hydroxyl-covered interface. The catalytic mechanisms of CO2 conversion to methanol at the dry and hydroxylated Cu4/γ-Al2O3 interfaces via the formate route and the pathway initiated through the hydrogenation of carbon monoxide produced by the reverse water–gas shift reaction are further explored. On both interfaces, the formate pathway is identified as the preferred reaction pathway, in which the hydrogenation of HCOO to H2COO is the rate-limiting step (RLS). However, since the surface OH group can act as a hydrogen source in some elementary reactions, unlike the dry surface, the production of H2COOH species along the formate pathway is found at the hydroxylated interface. In addition, the introduction of OH at the interface leads to an increase in the kinetic barrier of the RLS, indicating that surface hydroxylation has a negative effect on the catalytic activity of CO2 conversion to CH3OH at the Cu/γ-Al2O3 interface. Full article
(This article belongs to the Special Issue Theory-Guided Electrocatalysis and Photocatalysis)
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13 pages, 3063 KiB  
Article
Optimized Ni, Co, Mn Oxides Anchored on Graphite Plates for Highly Efficient Overall Water Splitting
by Jie Lin, Yihong Ding, Huile Jin and Tianbiao Zeng
Catalysts 2023, 13(7), 1031; https://doi.org/10.3390/catal13071031 - 23 Jun 2023
Cited by 3 | Viewed by 972
Abstract
Nickel, cobalt, and manganese oxides are easily obtainable non-noble metal catalysts for water splitting. However, the relationship between composition and catalysts’ performance still needs systematic studies. Herein, guided by theoretical calculations, a low overpotential, easily prepared Mn-doped Co3O4 was deposited [...] Read more.
Nickel, cobalt, and manganese oxides are easily obtainable non-noble metal catalysts for water splitting. However, the relationship between composition and catalysts’ performance still needs systematic studies. Herein, guided by theoretical calculations, a low overpotential, easily prepared Mn-doped Co3O4 was deposited on graphite plates for water splitting. The 30% Mn-doped Co3O4 (Co2.1Mn0.9O4) required the lowest overpotential for oxygen evolution reaction (OER), in which the Co2.1Mn0.9O4 reached 20, 30, and 50 mA cm−2 in the overpotentials of 425, 451, and 487 mV, respectively, with 90% IR compensation. Under overall water-splitting conditions, the current density reached 30 mA cm−2 at an overpotential of 0.78 V without IR compensation. Charge density difference analysis illustrates that doped Mn provides electrons for O atoms, and that Mn doping also promotes the electron fluctuation of Co atoms. XPS analysis reveals that Mn-doping increases the chemical valence of the Co atom, and that the doped Mn atom also exhibits higher chemical valence than the Mn of Mn3O4, which is advantageous to boost the form of based-OOH* radical, then decrease the overpotential. Considering the particular simplicity of growing the Co2.1Mn0.9O4 on graphite plates, this work is expected to provide a feasible way to develop the high-performance Co-Mn bimetallic oxide for water splitting. Full article
(This article belongs to the Special Issue Theory-Guided Electrocatalysis and Photocatalysis)
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12 pages, 3872 KiB  
Article
Tailoring of Three-Atom Metal Cluster Catalysts for Ammonia Synthesis
by Shuo Wang, Tingting Zhao and Likai Yan
Catalysts 2023, 13(5), 869; https://doi.org/10.3390/catal13050869 - 11 May 2023
Cited by 6 | Viewed by 1596
Abstract
Electrocatalytic nitrogen reduction reaction (NRR) can realize the green production of ammonia while developing electrocatalysts with high selectivity and ability is still an ongoing challenge. Two-dimensional (2D) graphitic carbon nitride (CN) frameworks can provide abundant hollow sites for stably anchoring several transition metal [...] Read more.
Electrocatalytic nitrogen reduction reaction (NRR) can realize the green production of ammonia while developing electrocatalysts with high selectivity and ability is still an ongoing challenge. Two-dimensional (2D) graphitic carbon nitride (CN) frameworks can provide abundant hollow sites for stably anchoring several transition metal (TM) atoms to facilitate single-cluster catalysis, promising to overcome the problems of low activity and poor selectivity in the process of ammonia synthesis. Herein, extensive density functional theory (DFT) calculations were performed to investigate the feasibility of six bimetallic triatomic clusters FexMoy (x = 1, 2; x + y = 3) supported on C6N6, C2N, and N-doped porous graphene (NG) as NRR electrocatalysts. Through a systematic screening strategy, we found that the Fe2Mo–NG possesses the highest activity with a limiting potential of –0.36 V through the enzymatic mechanism and could be the promising catalyst for NH3 synthesis. The Fe2Mo moiety in Fe2Mo–NG moderately regulates the electron transfer between reaction intermediates and NG, which is ascribed to enhanced performance. This work accelerates the rational design of catalysts in the field of NRR and contributes to broadening the understanding of cluster catalysis. Full article
(This article belongs to the Special Issue Theory-Guided Electrocatalysis and Photocatalysis)
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12 pages, 2046 KiB  
Article
Computational Study on the Catalytic Performance of Single-Atom Catalysts Anchored on g-CN for Electrochemical Oxidation of Formic Acid
by Abdul Qadeer, Meiqi Yang, Yuejie Liu, Qinghai Cai and Jingxiang Zhao
Catalysts 2023, 13(1), 187; https://doi.org/10.3390/catal13010187 - 13 Jan 2023
Cited by 1 | Viewed by 1722
Abstract
The electrochemical formic acid oxidation reaction (FAOR) has attracted great attention due to its high volumetric energy density and high theoretical efficiency for future portable electronic applications, for which the development of highly efficient and low-cost electrocatalysts is of great significance. In this [...] Read more.
The electrochemical formic acid oxidation reaction (FAOR) has attracted great attention due to its high volumetric energy density and high theoretical efficiency for future portable electronic applications, for which the development of highly efficient and low-cost electrocatalysts is of great significance. In this work, taking single-atom catalysts (SACs) supported on graphitic carbon nitrides (g-CN) as potential catalysts, their catalytic performance for the FAOR was systemically explored by means of density functional theory computations. Our results revealed that the strong hybridization with the unpaired lone electrons of N atoms in the g-CN substrate ensured the high stability of these anchored SACs and endowed them with excellent electrical conductivity. Based on the computed free energy changes of all possible elementary steps, we predicted that a highly efficient FAOR could be achieved on Ru/g-CN with a low limiting potential of −0.15 V along a direct pathway of HCOOH(aq) → HCOOH* → HCOO* → CO2* → CO2(g), in which the formation of HCOO* was identified as the potential-determining step, while the rate-determining step was located at the CO2* formation, with a moderate kinetic barrier of 0.89 eV. Remarkably, the moderate d-band center and polarized charge of the Ru active site caused the Ru/g-CN catalyst to exhibit an optimal binding strength with various reaction intermediates, explaining well its superior FAOR catalytic performance. Hence, the single Ru atom anchored on g-CN could be utilized as a promising SAC for the FAOR, which opens a new avenue to further develop novel catalysts for a sustainable FAOR in formic-acid-based fuel cells. Full article
(This article belongs to the Special Issue Theory-Guided Electrocatalysis and Photocatalysis)
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12 pages, 2367 KiB  
Article
Novel Bifunctional Nitrogen Doped MoS2/COF-C4N Vertical Heterostructures for Electrocatalytic HER and OER
by Nan Zhang, Zhaodi Yang, Wenshan Liu, Fengming Zhang and Hong Yan
Catalysts 2023, 13(1), 90; https://doi.org/10.3390/catal13010090 - 01 Jan 2023
Cited by 8 | Viewed by 2167
Abstract
Highly active and earth-abundant catalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) play vital roles in developing efficient water splitting to produce hydrogen fuels. Here, we reported an effective strategy to fabricate a completely new nitrogen-doped MoS2/COF-C4 [...] Read more.
Highly active and earth-abundant catalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) play vital roles in developing efficient water splitting to produce hydrogen fuels. Here, we reported an effective strategy to fabricate a completely new nitrogen-doped MoS2/COF-C4N vertical heterojunction (N-MoS2/COF-C4N) as precious-metal-free bifunctional electrocatalysts for both HER and OER. Compared with MoS2 and COF-C4N, the obtained vertical N-MoS2/COF-C4N catalyst showed enhanced HER with a low overpotential of 106 mV at 10 mA cm−2, which is six times lower than MoS2. The superior acidic HER activity, molecular mechanism, and charge transfer characteristic of this vertical N-MoS2/COF-C4N were investigated experimentally and theoretically in detail. Its basic OER activity is almost equal to that of COF-C4N with an overpotential of 349 mV at 10 mA cm−2, which showed that the in-situ growing method maintains the exposure of the C active sites to the greatest extent. The preparation and investigation for vertical N-MoS2/COF-C4N provide ideas and a research basis for us to further explore promising overall water-splitting electrocatalysts. Full article
(This article belongs to the Special Issue Theory-Guided Electrocatalysis and Photocatalysis)
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11 pages, 2662 KiB  
Article
Nitrogen Reduction Reaction Catalyzed by Diatomic Metals Supported by N-Doped Graphite
by Jinrong Huo, Haocong Wei, Kai Zhang, Chenxu Zhao and Chaozheng He
Catalysts 2023, 13(1), 49; https://doi.org/10.3390/catal13010049 - 26 Dec 2022
Cited by 1 | Viewed by 1484
Abstract
In this article, for the transition metal-nitrogen ligand Mn-M@N6-C (M = Ag, Bi, Cd, Co, Cr, Cu, Fe, Hf, Ir, Mo, Nb, Ni, Os, Pd, Pt, Re, Rh, Ru, Sc, Ta, Tc, V, Y, Zn, Zr, Ti, W), by comparing the [...] Read more.
In this article, for the transition metal-nitrogen ligand Mn-M@N6-C (M = Ag, Bi, Cd, Co, Cr, Cu, Fe, Hf, Ir, Mo, Nb, Ni, Os, Pd, Pt, Re, Rh, Ru, Sc, Ta, Tc, V, Y, Zn, Zr, Ti, W), by comparing the amount of change in the length of the N-N triple-bond, and calculating the adsorption energy of N2 and the change of charge around N2, it is shown that the activation effect of Sc, Ti, Y, Nb-Mn@N6-C on the single-atomic layer of graphite substrate is relatively good. The calculation of structural stability shows that the Mn-M@N6-C (M = Sc, Ti, Y) load is relatively stable when it is on the single-atomic layer of the graphite substrate. Through calculations, a series of data such as the adsorption free energy and reaction path are obtained, and the final results show that the preferred reaction mechanism of NRR is the alternating path on Mn-Ti@N6-C, and the reaction limit potential is only 0.16 eV, Mn-Ti@N6-C and has good NRR activity. In addition, the vertical path on Mn-Y@N6-C has a reaction limit potential of 0.39 eV. Mn-Y@N6-C also has good NRR catalyzing activity. Full article
(This article belongs to the Special Issue Theory-Guided Electrocatalysis and Photocatalysis)
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