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Materials
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Transition Metal Nanomaterials: Synthesis and Photo/Electrocatalytic Performance
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Transition Metal Nanomaterials: Synthesis and Photo/Electrocatalytic Performance

A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: 20 March 2025 | Viewed by 2957

Special Issue Editor

Dr. Ellie Uzunova

E-Mail Website
Guest Editor
Institute of General and Inorganic Chemistry Bulgarian Academy of Sciences, Sofia, Bulgaria
Interests: computational chemistry; ab initio studies; transition metal oxides; chalcogenides; photoactivation; catalysis

Special Issue Information

Dear Colleagues,

The design of efficient photo/electrocatalysts for the production of fuel from renewable sources (water decomposition, carbon dioxide reduction) is an expanding area of research. TiO2 was among the prospective electrocatalysts for water splitting. Cuprous oxide (Cu2O) adsorbs water dissociatively, and also proved promising in carbon dioxide reduction. A well-known bottleneck of the electrochemical water dissociation is the high overpotential for OER, the oxygen evolution reaction. Two major trends in the development of photo/electrocatalysts emerged: (1) the synthesis of nanomaterials and layered 2D (two-dimensional) solid films, and (2) the synthesis of compounds, which are analogues of natural enzymes (hydrogenase, carbon monoxide dehydrogenase) aiming at artificial photosynthesis. A number of properties need to be monitored when changing from bulk to nanomaterials or layers: the band gaps, the number and type of defects, the ability to accept and donate electrons. For transition metal oxides it proved useful to link nanoparticles to a light absorber, while chalcogenides may provide themselves favorable light absorption bands. Theoretical models help in the predictability of potentially active photo-electro catalysts. 

There are certainly more redox reactions which benefit from the design of efficient photoelectrochemical cell.

I kindly invite you to submit a manuscript for this Special Issue. Full papers, communications, and reviews are all welcome.

Dr. Ellie Uzunova
Guest Editor

Manuscript Submission Information

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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. Materials is an international peer-reviewed open access semimonthly journal published by MDPI.

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Keywords

  • light absorbers
  • OER (Oxygen evolution reaction)
  • HER (Hydrogen evolution reaction)
  • CO2 reduction
  • photoactivated electrochemical redox reactions
  • artificial photosynthesis
  • 2D (two-dimensional) transition metal compounds
  • quantum chemical modeling of photoactive electrocatalysts

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Published Papers (3 papers)

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Research

9 pages, 1716 KiB  
Article
Adsorption and Catalytic Reduction of Nitrogen Oxides (NO, N2O) on Disulfide Cluster Complexes of Cobalt and Iron—A Density Functional Study
by Ellie L. Uzunova and Ivelina M. Georgieva
Materials 2024, 17(19), 4764; https://doi.org/10.3390/ma17194764 - 28 Sep 2024
Viewed by 590
Abstract
The reactivity of nitrogen oxide, NO, as a ligand in complexes with [Fe2-S2] and [Co2-S2] non-planar rhombic cores is examined by density functional theory (DFT). The cobalt-containing nitrosyl complexes are less stable than the iron complexes because the Co-S bonds in the [Co2-S2] [...] Read more.
The reactivity of nitrogen oxide, NO, as a ligand in complexes with [Fe2-S2] and [Co2-S2] non-planar rhombic cores is examined by density functional theory (DFT). The cobalt-containing nitrosyl complexes are less stable than the iron complexes because the Co-S bonds in the [Co2-S2] core are weakened upon NO coordination. Various positions of NO were examined, including its binding to sulfur centers. The release of NO molecules can be monitored photochemically. The ability of NO to form a (NO)2 dimer provides a favorable route of electrochemical reduction, as protonation significantly stabilizes the dimeric species over the monomers. The quasilinear dimer ONNO, with trans-orientation of oxygen atoms, gains higher stability under protonation and reduction via proton–electron transfer. The first two reduction steps lead to an N2O intermediate, whose reduction is more energy demanding: in the two latter reaction steps the highest energy barrier for Co2S2(CO)6 is 109 kJ mol−1, and for Fe2S2(CO)6, it is 133 kJ mol−1. Again, the presence of favorable light absorption bands allows for a photochemical route to overcome these energy barriers. All elementary steps are exothermic, and the final products are molecular nitrogen and water. Full article
(This article belongs to the Special Issue Transition Metal Nanomaterials: Synthesis and Photo/Electrocatalytic Performance)
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13 pages, 3834 KiB  
Article
Upcycling of Cr-Containing Sulfate Waste into Efficient FeCrO3/Fe2O3 Catalysts for CO2 Hydrogenation Reaction
by Yongqi Liu, Shasha Chu, Yuebing Xu, Xinyu Chen, Hao Zhou, Jinlin Li, Yanjie Ren and Xintai Su
Materials 2024, 17(7), 1598; https://doi.org/10.3390/ma17071598 - 31 Mar 2024
Cited by 1 | Viewed by 959
Abstract
Upcycling Cr-containing sulfate waste into catalysts for CO2 hydrogenation reaction benefits both pollution mitigation and economic sustainability. In this study, FeCrO3/Fe2O3 catalysts were successfully prepared by a simple hydrothermal method using Cr-containing sodium sulfate (Cr-SS) as a [...] Read more.
Upcycling Cr-containing sulfate waste into catalysts for CO2 hydrogenation reaction benefits both pollution mitigation and economic sustainability. In this study, FeCrO3/Fe2O3 catalysts were successfully prepared by a simple hydrothermal method using Cr-containing sodium sulfate (Cr-SS) as a Cr source for efficient conversion and stable treatment of Cr. The removal rate of Cr in Cr-SS can reach 99.9% at the optimized hydrothermal conditions. When the synthesized catalysts were activated and used for the CO2 hydrogenation reaction, a 50% increase in CO2 conversion was achieved compared with the catalyst prepared by impregnation with a comparable amount of Cr. According to the extraction and risk assessment code (RAC) of the Reference Office of the European Community Bureau (BCR), the synthesized FeCrO3/Fe2O3 is risk-free. This work not only realizes the detoxification of the Cr-SS but transfers Cr into stable FeCrO3 for application in a catalytic field, which provides a strategy for the harmless disposal and resource utilization of Cr-containing hazardous waste. Full article
(This article belongs to the Special Issue Transition Metal Nanomaterials: Synthesis and Photo/Electrocatalytic Performance)
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11 pages, 4341 KiB  
Article
Solution Combustion Synthesis of Ni-Based Nanocatalyst Using Ethylenediaminetetraacetic Acid and Nickel-Carbon Nanotube Growth Behavior
by Juyoung Kim, Hwanseok Lee, Jaekwang Lee, Hyunjo Yoo, Ilguk Jo and Heesoo Lee
Materials 2023, 16(22), 7191; https://doi.org/10.3390/ma16227191 - 16 Nov 2023
Viewed by 991
Abstract
We studied the influence of the ethylenediaminetetraacetic acid (EDTA) content used as combustion fuel when fabricating nickel oxide (NiO) nanocatalysts via solution combustion synthesis, as well as the growth behavior of carbon nanotubes (CNTs) using this catalyst. Nickel nitrate hexahydrate (Ni(NO3) [...] Read more.
We studied the influence of the ethylenediaminetetraacetic acid (EDTA) content used as combustion fuel when fabricating nickel oxide (NiO) nanocatalysts via solution combustion synthesis, as well as the growth behavior of carbon nanotubes (CNTs) using this catalyst. Nickel nitrate hexahydrate (Ni(NO3)2∙6H2O) was used as the metal precursor (an oxidizer), and the catalysts were synthesized by adjusting the molar ratio of fuel (EDTA) to oxidizer in the range of 1:0.25 to 2.0. The results of the crystal structure analysis showed that as the EDTA content increased beyond the chemical stoichiometric balance with Ni(NO3)2∙6H2O (F/O = 0.25), the proportion of Ni metal within the catalyst particles decreased, and only single-phase NiO was observed. Among the synthesized catalysts, the smallest crystallite size was observed with a 1:1 ratio of Ni ions to EDTA. However, an increase in the amount of EDTA resulted in excessive fuel supply, leading to an increase in crystallite size. Microstructure analysis revealed porous NiO agglomerates due to the use of EDTA, and differences in particle growth based on the fuel ratio were observed. We analyzed the growth behavior of CNTs grown using NiO nanocatalysts through catalytic chemical vapor deposition (CCVD). As the F/O ratio increased, it was observed that the catalyst particles grew excessively beyond hundreds of nanometers, preventing further CNT growth and leading to a rapid termination of CNT growth. Raman spectroscopy was used to analyze the structural characteristics of CNTs, and it was found that the ID/IG ratio indicated the highest CNT crystallinity near an F/O ratio of 1:1. Full article
(This article belongs to the Special Issue Transition Metal Nanomaterials: Synthesis and Photo/Electrocatalytic Performance)
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