10th Anniversary of Catalysts: Achievements in Electrocatalysis for Sustainable Energy Technologies

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

Deadline for manuscript submissions: closed (31 December 2021) | Viewed by 22183

Special Issue Editors

CNR-ITAE Institute for Advanced Energy Technologies “N. Giordano”, Via Salita S. Lucia sopra Contesse 5, 98126 Messina, Italy
Interests: polymer electrolyte fuel cells; direct alcohol fuel cells; water electrolysis; metal–air batteries; dye-sensitized solar cells; photo-electrolysis; carbon dioxide electro-reduction
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Department of Chemical and Biomolecular Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
Interests: electrocatalysis; oxygen reduction reaction; carbon dioxide reduction; lithium ion batteries; lithium air batteries; fuel cells; DFT calculations
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Department of Materials Science, University of Milano-Bicocca, U5 Via Cozzi 55, 20125 Milan, Italy
Interests: environmental engineering; electrochemistry; chemistry and microbiology; renewable energies for energy production; wastewater treatment; hydrogen evolution and water desalination; inorganic and abiotic materials (nanostructured and porous carbons, platinum group metals-free (PGM‐Free) catalysts) synthesis and characterization for sustainable bio-electrochemical systems and oxygen reduction reaction; hydrogen evolution reaction and CO2 electroreduction; supercapacitors for energy storage; electroactive biofilm formation and characterization; functionalization of bio-char for specific reactions; device engineering: from single components to overall system
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Institute of Carbochemistry, CSIC-Spanish National Research Council, C/. Miguel Luesma Castán, 4, 50018 Zaragoza, Spain
Interests: energy and environment; catalysis; carbon materials; graphene; carbon nanofibers; electrochemistry; fuel cells; water electrolysis; carbon dioxide electro-reduction
Special Issues, Collections and Topics in MDPI journals
State Key Laboratory of Environment-Friendly Energy Materials, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China
Interests: electrocatalysis; porous materials; advanced energy materials

Special Issue Information

Dear Colleagues,

On the occasion of the 10th Anniversary of the journal Catalysts, we would like to collect the most recent advances on electrocatalysis for sustainable energy technologies, such as fuel cells, electrolyzers, metal–air batteries, photo-electrochemical cells, dye-sensitized solar cells, and bioelectrochemical systems (microbial and enzymatic), among others. It is claimed that such devices will dominate the power supply market in the future sustainable energy economy. The practical efficiencies must still be boosted before many of the aforementioned technologies become viable for large-scale use. In particular, more active, stable, and economically viable electro-catalysts must be developed for the electrocatalytic processes occurring at the practical electrodes of the cells. In this context, the research and development of efficient catalysts are key points to reach this target. Full-length papers, short communications, and review articles are warmly invited for this Special Issue.

Dr. Vincenzo Baglio
Dr. Minhua Shao
Dr. Carlo Santoro
Dr. David Sebastián
Prof. Dr. Yingze Song
Guest Editors

Manuscript Submission Information

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Keywords

  • Polymer electrolyte and direct alcohol fuel cells (PEFC and DAFC)
  • Solid oxide fuel cells (SOFC)
  • Polymer electrolyte and solid oxide electrolyzers
  • Metal–air batteries
  • Photo-electrochemical cells
  • Microbial electrochemical systems
  • Enzymatic electrochemical systems
  • Advances in the design and synthesis of electrocatalysts
  • Advanced carbonaceous, non-carbonaceous, and hybrid support for electrocatalysts
  • Oxygen reduction and/or evolution reactions
  • Electro-oxidation of alcohols and other organic fuels
  • Hydrogen oxidation and/or evolution reactions

Published Papers (8 papers)

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Research

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13 pages, 2231 KiB  
Article
Influence of Nitrogen and Sulfur Doping of Carbon Xerogels on the Performance and Stability of Counter Electrodes in Dye Sensitized Solar Cells
by Cinthia Alegre, David Sebastián, María Jesús Lázaro, Mariarita Girolamo, Antonino Salvatore Aricò and Vincenzo Baglio
Catalysts 2022, 12(3), 264; https://doi.org/10.3390/catal12030264 - 25 Feb 2022
Cited by 8 | Viewed by 2005
Abstract
In this work, carbon xerogels (CXGs) doped with nitrogen or sulfur have been investigated as DSSC counter electrodes. CXGs have been prepared by a sol–gel method from resorcinol and formaldehyde and subsequent carbonization. Nitrogen doping has been carried out by introducing melamine into [...] Read more.
In this work, carbon xerogels (CXGs) doped with nitrogen or sulfur have been investigated as DSSC counter electrodes. CXGs have been prepared by a sol–gel method from resorcinol and formaldehyde and subsequent carbonization. Nitrogen doping has been carried out by introducing melamine into the synthesis process along with resorcinol and formaldehyde, while sulfur has been incorporated by direct reaction of the carbon material with elemental sulfur. The counter electrodes for DSSCs have been prepared by airbrushing on conductive glass (fluorine-doped tin oxide, FTO), and their electrochemical behavior has been evaluated, observing that the introduction of heteroatoms such as nitrogen or sulfur leads to an improvement in efficiency compared to the undoped material thanks to a decrease in charge transfer resistance. Full article
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16 pages, 3087 KiB  
Article
PdAg/C Electrocatalysts Synthesized by Thermal Decomposition of Polymeric Precursors Improve Catalytic Activity for Ethanol Oxidation Reaction
by Yonis Fornazier Filho, Ana Caroliny Carvalho da Cruz, Rolando Pedicini, José Ricardo Cezar Salgado, Rodrigo Vieira Rodrigues, Priscilla Paiva Luz, Sergi Garcia-Segura and Josimar Ribeiro
Catalysts 2022, 12(1), 96; https://doi.org/10.3390/catal12010096 - 14 Jan 2022
Cited by 4 | Viewed by 1936
Abstract
An efficient ethanol oxidation reaction (EOR) is required to enhance energy production in alcohol-based fuel cells. The use of bimetallic catalysts promises decreasing reliance on platinum group metal (PGM) electrocatalysts by minimizing the use of these expensive materials in the overall electrocatalyst composition. [...] Read more.
An efficient ethanol oxidation reaction (EOR) is required to enhance energy production in alcohol-based fuel cells. The use of bimetallic catalysts promises decreasing reliance on platinum group metal (PGM) electrocatalysts by minimizing the use of these expensive materials in the overall electrocatalyst composition. In this article, an alternative method of bimetallic electrocatalyst synthesis based on the use of polymeric precursors is explored. PdAg/C electrocatalysts were synthesized by thermal decomposition of polymeric precursors and used as the anode electrocatalyst for EOR. Different compositions, including pristine Pd/C and Ag/C, as well as bimetallic Pd80Ag20/C, and Pd60Ag40/C electrocatalysts, were evaluated. Synthesized catalysts were characterized, and electrochemical activity evaluated. X-ray diffraction showed a notable change at diffraction peak values for Pd80Ag20/C and Pd60Ag40/C electrocatalysts, suggesting alloying (solid solution) and smaller crystallite sizes for Pd60Ag40/C. In a thermogravimetric analysis, the electrocatalyst Pd60Ag40/C presented changes in the profile of the curves compared to the other electrocatalysts. In the cyclic voltammetry results for EOR in alkaline medium, Pd60Ag40/C presented a more negative onset potential, a higher current density at the oxidation peak, and a larger electrically active area. Chronoamperometry tests indicated a lower poisoning rate for Pd60Ag40/C, a fact also observed in the CO-stripping voltammetry analysis due to its low onset potential. As the best performing electrocatalyst, Pd60Ag40/C has a lower mass of Pd (a noble and expensive metal) in its composition. It can be inferred that this bimetallic composition can contribute to decreasing the amount of Pd required while increasing the fuel cell performance and expected life. PdAg-type electrocatalysts can provide an economically feasible alternative to pure PGM-electrocatalysts for use as the anode in EOR in fuel cells. Full article
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17 pages, 4059 KiB  
Article
“Doing More with Less”: Ni(II)@ORMOSIL, a Novel Sol-Gel Pre-Catalyst for the Reduction of Nitrobenzene
by Michael Meistelman, Dan Meyerstein, Ariela Burg, Dror Shamir and Yael Albo
Catalysts 2021, 11(11), 1391; https://doi.org/10.3390/catal11111391 - 18 Nov 2021
Cited by 4 | Viewed by 1902
Abstract
Reduction of nitrobenzene with NaBH4 using zero-valent iron nanoparticles (ZVI-NPs) and NiCl2∙6H2O incorporated in organically modified hybrid silica matrices as ZVI@ORMOSIL and Ni(II)@ORMOSIL catalysts is proposed as a remediation strategy. Ni(II)@ORMOSIL is prepared by ion-exchanging H+ of [...] Read more.
Reduction of nitrobenzene with NaBH4 using zero-valent iron nanoparticles (ZVI-NPs) and NiCl2∙6H2O incorporated in organically modified hybrid silica matrices as ZVI@ORMOSIL and Ni(II)@ORMOSIL catalysts is proposed as a remediation strategy. Ni(II)@ORMOSIL is prepared by ion-exchanging H+ of the ORMOSIL matrix with NiII. Ni(II)@ORMOSIL is a pre-catalyst that undergoes reduction by NaBH4 by an in-situ reaction and promotes nitrobenzene reduction by the unconsumed NaBH4, leading to sparing use of the catalyst. Ni(II)@ORMOSIL undergoes color change from green to black in this process, returning to a green hue after washing and drying. Nitrobenzene reductions were examined in aqueous acetonitrile solvent mixtures, and the reduction cascade produced the reaction end-products with catalytic implications. Plausible mechanisms of ZVI@ORMOSIL and Ni(II)@ORMOSIL catalyzed reductions of nitrobenzene are discussed. This work is the first to report M(II)@ORMOSIL pre-catalysts for in-situ reduction of nitrobenzene, and expands the scope of the ORMOSIL series of catalysts for the reduction of polluting compounds. This approach enables the development of catalysts that use very low concentrations of transition metal cations. Full article
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11 pages, 3481 KiB  
Article
Evaluation of Goethite as a Catalyst for the Thermal Stage of the Westinghouse Process for Hydrogen Production
by Carmen M. Fernández-Marchante, Alexandra Raschitor, Ismael F. Mena, Manuel A. Rodrigo and Justo Lobato
Catalysts 2021, 11(10), 1145; https://doi.org/10.3390/catal11101145 - 24 Sep 2021
Cited by 1 | Viewed by 1698
Abstract
This work focuses on the evaluation of goethite as a catalyst for the transformation of sulfuric acid into sulfur dioxide, a reaction with great interest for the hybrid electrochemical-thermoelectrochemical Westinghouse cycle for hydrogen production. A comparison of the performance of goethite with that [...] Read more.
This work focuses on the evaluation of goethite as a catalyst for the transformation of sulfuric acid into sulfur dioxide, a reaction with great interest for the hybrid electrochemical-thermoelectrochemical Westinghouse cycle for hydrogen production. A comparison of the performance of goethite with that of CuO, Fe2O3, and SiC has been carried out. Moreover, a mixture of those catalysts was evaluated. The results demonstrate that goethite can be used as a catalyst for the thermal decomposition of sulfuric acid in the Westinghouse cycle, with an activity higher than that of SiC but lower than that of Fe2O3 and CuO. However, it does not undergo sintering during its use, but just produces small particles in its surface, which remain after the treatment. Mixtures of Fe2O3 with SiC or goethite do not produce synergism, thus operating each catalyst in an independent way. Full article
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13 pages, 1571 KiB  
Article
Indigo-Mediated Semi-Microbial Biofuel Cell Using an Indigo-Dye Fermenting Suspension
by Mayu Kikuchi, Keisei Sowa, Kasumi Nakagawa, Momoka Matsunaga, Akinori Ando, Kenji Kano, Michiki Takeuchi and Eiji Sakuradani
Catalysts 2021, 11(9), 1080; https://doi.org/10.3390/catal11091080 - 08 Sep 2021
Cited by 1 | Viewed by 2936
Abstract
Aizome (Japanese indigo dyeing) is a unique dyeing method using microbial activity under anaerobic alkaline conditions. In indigo-dye fermenting suspensions; microorganisms reduce indigo into leuco-indigo with acetaldehyde as a reductant. In this study; we constructed a semi-microbial biofuel cell using an indigo-dye fermenting [...] Read more.
Aizome (Japanese indigo dyeing) is a unique dyeing method using microbial activity under anaerobic alkaline conditions. In indigo-dye fermenting suspensions; microorganisms reduce indigo into leuco-indigo with acetaldehyde as a reductant. In this study; we constructed a semi-microbial biofuel cell using an indigo-dye fermenting suspension. Carbon fiber and Pt mesh were used as the anode and cathode materials, respectively. The open-circuit voltage (OCV) was 0.6 V, and the maximum output power was 32 µW cm−2 (320 mW m−2). In addition, the continuous stability was evaluated under given conditions starting with the highest power density; the power density rapidly decreased in 0.5 h due to the degradation of the anode. Conversely, at the OCV, the anode potential exhibited high stability for two days. However, the OCV decreased by approximately 80 mV after 2 d compared with the initial value, which was attributed to the performance degradation of the gas-diffusion-cathode system caused by the evaporation of the dispersion solution. This is the first study to construct a semi-microbial biofuel cell using an indigo-dye fermenting suspension. Full article
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15 pages, 3227 KiB  
Communication
Electrodeposition of Fe-Complexes on Oxide Surfaces for Efficient OER Catalysis
by Sahir M. Al-Zuraiji, Tímea Benkó, Krisztina Frey, Zsolt Kerner and József S. Pap
Catalysts 2021, 11(5), 577; https://doi.org/10.3390/catal11050577 - 30 Apr 2021
Cited by 10 | Viewed by 2718
Abstract
Progress in non-covalent/self-assembled immobilization methods on (photo)electrode materials for molecular catalysts could broaden the scope of attainable systems. While covalent linkage (though considered more stable) necessitates functional groups introduced by means of often cumbersome synthetic procedures, non-covalent assemblies require sufficient propensity of the [...] Read more.
Progress in non-covalent/self-assembled immobilization methods on (photo)electrode materials for molecular catalysts could broaden the scope of attainable systems. While covalent linkage (though considered more stable) necessitates functional groups introduced by means of often cumbersome synthetic procedures, non-covalent assemblies require sufficient propensity of the molecular unit for surface adsorption, thus set less rigorous pre-requisites. Herein, we report efficient electrodeposition (ED) of two Fe(III) complexes prepared with closely related NN’N pincer ligands yielding stable and active ad-layers for the electrocatalysis of the oxygen-evolving reaction (OER). The ED method is based on the utilization of a chloride precursor complex [FeIIICl2(NN’N)], which is dissolved in an organic electrolyte undergoes chloride/aqua ligand exchange upon addition of water. ED provides patchy distribution of a chloride-depleted catalyst layer on indium tin oxide (ITO) and fluorine-doped tin oxide (FTO) surfaces, which can be applied for long periods as OER electrocatalysts. Compared to drop-casting or layering of [FeIIICl2(NN’N)] with Nafion (a commonly used support for molecular electrocatalysts), the surface modification by ED is a material saving and efficient method to immobilize catalysts. Full article
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20 pages, 4526 KiB  
Article
Na3[Ru2(µ-CO3)4] as a Homogeneous Catalyst for Water Oxidation; HCO3 as a Co-Catalyst
by Shanti Gopal Patra, Totan Mondal, Krishnamoorthy Sathiyan, Amir Mizrahi, Haya Kornweitz and Dan Meyerstein
Catalysts 2021, 11(2), 281; https://doi.org/10.3390/catal11020281 - 21 Feb 2021
Cited by 9 | Viewed by 2942
Abstract
In neutral medium (pH 7.0) [RuIIIRuII(µ-CO3)4(OH)]4− undergoes one electron oxidation to form [RuIIIRuIII(µ-CO3)4(OH)2]4− at an E1/2 of 0.85 [...] Read more.
In neutral medium (pH 7.0) [RuIIIRuII(µ-CO3)4(OH)]4− undergoes one electron oxidation to form [RuIIIRuIII(µ-CO3)4(OH)2]4− at an E1/2 of 0.85 V vs. NHE followed by electro-catalytic water oxidation at a potential ≥1.5 V. When the same electrochemical measurements are performed in bicarbonate medium (pH 8.3), the complex first undergoes one electron oxidation at an Epa of 0.86 V to form [RuIIIRuIII(µ-CO3)4(OH)2]4−. This complex further undergoes two step one electron oxidations to form RuIVRuIII and RuIVRuIV species at potentials (Epa) 1.18 and 1.35 V, respectively. The RuIVRuIII and RuIVRuIV species in bicarbonate solutions are [RuIVRuIII(µ-CO3)4(OH)(CO3)]4− and [RuIVRuIV(µ-CO3)4(O)(CO3)]4− based on density functional theory (DFT) calculations. The formation of HCO4 in the course of the oxidation has been demonstrated by DFT. The catalyst acts as homogeneous water oxidation catalyst, and after long term chronoamperometry, the absorption spectra does not change significantly. Each step has been found to follow a proton coupled electron transfer process (PCET) as obtained from the pH dependent studies. The catalytic current is found to follow linear relation with the concentration of the catalyst and bicarbonate. Thus, bicarbonate is involved in the catalytic process that is also evident from the generation of higher oxidation peaks in cyclic voltammetry. The detailed mechanism has been derived by DFT. A catalyst with no organic ligands has the advantage of long-time stability. Full article
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Review

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18 pages, 3470 KiB  
Review
A Brief Review of Catalytic Cathode Materials for Na-CO2 Batteries
by Dong Sui, Meijia Chang, Haiyu Wang, Hang Qian, Yanliang Yang, Shan Li, Yongsheng Zhang and Yingze Song
Catalysts 2021, 11(5), 603; https://doi.org/10.3390/catal11050603 - 07 May 2021
Cited by 35 | Viewed by 4514
Abstract
As an emerging energy storage technology, Na-CO2 batteries with high energy density are drawing tremendous attention because of their advantages of combining cost-effective energy conversion and storage with CO2 clean recycle and utilization. Nevertheless, their commercial applications are impeded by unsatisfactory [...] Read more.
As an emerging energy storage technology, Na-CO2 batteries with high energy density are drawing tremendous attention because of their advantages of combining cost-effective energy conversion and storage with CO2 clean recycle and utilization. Nevertheless, their commercial applications are impeded by unsatisfactory electrochemical performance including large overpotentials, poor rate capability, fast capacity deterioration, and inferior durability, which mainly results from the inefficient electrocatalysts of cathode materials. Therefore, novel structured cathode materials with efficient catalytic activity are highly desired. In this review, the latest advances of catalytic cathode materials for Na-CO2 batteries are summarized, with a special emphasis on the electrocatalysts for CO2 reduction and evolution, the formation and decomposition of discharge product, as well as their catalytic mechanism. Finally, an outlook is also proposed for the future development of Na-CO2 batteries. Full article
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