Catalysts for Sustainable Hydrogen Production: Preparation, Applications and Process Integration, 2nd Edition

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

Deadline for manuscript submissions: closed (31 July 2023) | Viewed by 22368

Special Issue Editors


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Guest Editor
Department of Industrial Engineering, University of Salerno, Via Giovanni Paolo II, Fisciano, Italy
Interests: heterogeneous catalysts; hydrogen production; reforming; renewables conversion
Special Issues, Collections and Topics in MDPI journals

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Guest Editor
Energy Technology and Renewable Sources Department (TERIN)—ENEA—Italian National Agency for New Technologies, Energy and Sustainable Economic Development, Piazzale Enrico Fermi, 1, Località Granatello, 80055 Portici, Italy
Interests: hydrogen production and storage, reforming; gasification; propane dehydrogenation; structured catalysts
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The current Special Issue is a continuation of the previous successful SI entitled “Catalysts for Sustainable Hydrogen Production: Preparation, Applications and Process Integration”. Hydrogen is considered the most promising energy carrier for the transition to renewable energy sources, and in supporting the electrification of processes which require long-term energy storage. However, a number of problems related to the production, storage and transport of hydrogen are still not fully resolved. Furthermore, hydrogen is a strategic reagent for several production processes, such as hydrocarbon production processes, in addition to playing a role in CO2 capture and use. Thus, a wide range of hydrogen production processes and associated technologies have been identified as alternatives to the conventional unsustainable methods for H2 generation.

This Special Issue mainly refers to innovative options as well as green methods for clean hydrogen generation and application. Both review and original research articles focused on all aspects of heterogeneous catalysis are welcomed; topics include, but are not limited to, the following:

  • Catalytic biofuel reforming;
  • Catalytic water–gas shift;
  • Catalytic dry reforming;
  • New materials for catalytic H2 production;
  • Innovative materials for hydrogen storage;
  • Catalysts for fuel cells;
  • Catalysts for syngas methanation and hydrogenation;
  • Carbon capture, storage and utilization;
  • Advanced electrolysis;
  • Photolysis and biophotolysis of wastes and biomass;
  • Thermolysis and biothermolysis of wastes and biomass.

Dr. Concetta Ruocco
Dr. Marco Martino
Guest Editors

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Keywords

  • hydrogen
  • heterogeneous catalysis
  • biofuel reforming
  • dry reforming
  • hydrogen storage
  • water–gas shift
  • methanation and hydrogenation
  • electrolysis
  • carbon capture

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Published Papers (10 papers)

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Editorial

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3 pages, 155 KiB  
Editorial
Catalysts for Sustainable Hydrogen Production: Preparation, Applications and Process Integration, 2nd Edition
by Concetta Ruocco and Marco Martino
Catalysts 2024, 14(9), 565; https://doi.org/10.3390/catal14090565 - 26 Aug 2024
Viewed by 334
Abstract
The effects of climate change are now evident all over the world [...] Full article

Research

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20 pages, 3119 KiB  
Article
Influence of HB2Nb3O10-Based Nanosheet Photocatalysts (B = Ca, Sr) Preparation Method on Hydrogen Production Efficiency
by Sergei A. Kurnosenko, Vladimir V. Voytovich, Oleg I. Silyukov, Ivan A. Rodionov, Ekaterina N. Malygina and Irina A. Zvereva
Catalysts 2023, 13(3), 614; https://doi.org/10.3390/catal13030614 - 18 Mar 2023
Cited by 4 | Viewed by 1488
Abstract
Photocatalytic activity of HB2Nb3O10 perovskite nanosheets (B = Ca, Sr) has been systematically investigated in the reactions of hydrogen production, depending on the method of the photocatalyst preparation: using the pristine nanosheets in the parent suspension without reassembly, [...] Read more.
Photocatalytic activity of HB2Nb3O10 perovskite nanosheets (B = Ca, Sr) has been systematically investigated in the reactions of hydrogen production, depending on the method of the photocatalyst preparation: using the pristine nanosheets in the parent suspension without reassembly, filtered nanosheets as well as nanosheets restacked by hydrochloric acid. Photocatalytic measurements were organized in such a way as to control a wide range of parameters, including the hydrogen generation rate, quantum efficiency of the reaction, potential dark activity of the sample as well as stability and pH of the reaction suspension. Exfoliation of the niobates into nanosheets allowed obtaining efficient photocatalysts surpassing the initial bulk materials in the activity up to 55 times and providing apparent quantum efficiency up to 20.8% after surface decoration with a Pt cocatalyst. Among the reassembled samples, greater hydrogen evolution activity was exhibited by simply filtered nanosheets that, unlike the HCl-restacked ones, were found to possess much lower specific surface area in a dry state but contain a perceptible amount of tetrabutylammonium cations on the surface. The activity difference, potentially, is associated with the fact that the filtered nanosheets undergo ultrasonic disaggregation before photocatalytic tests much easier than their HCl-restacked counterparts and, thanks to this, have greater active surface in the reaction suspension. In addition, the enhanced activity of the filtered nanosheets may be due to the presence of tetrabutylammonium as an organic modifier on their surface, which is consistent with the high photocatalytic performance of organically modified layered perovskites considered in our previous reports. Full article
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14 pages, 2246 KiB  
Article
Superior Photocatalytic Activity of BaO@Ag3PO4 Nanocomposite for Dual Function Degradation of Methylene Blue and Hydrogen Production under Visible Light Irradiation
by Hanaa Selim, E. R. Sheha, Rania Elshypany, Patrice Raynaud, Heba H. El-Maghrabi and Amr A. Nada
Catalysts 2023, 13(2), 363; https://doi.org/10.3390/catal13020363 - 7 Feb 2023
Cited by 5 | Viewed by 1709
Abstract
The current work focuses on the photo degradation of organic pollutants, particularly methylene blue (MB) dye, and the production of hydrogen as green energy using a composite of silver phosphate Ag3PO4 (AP) and barium oxide/silver phosphate BaO@Ag3PO4 [...] Read more.
The current work focuses on the photo degradation of organic pollutants, particularly methylene blue (MB) dye, and the production of hydrogen as green energy using a composite of silver phosphate Ag3PO4 (AP) and barium oxide/silver phosphate BaO@Ag3PO4 (APB) as a photocatalyst. This composite was successfully synthesized using a chemical co-precipitation approach. The physicochemical properties of the obtained samples were investigated using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis/DRS), and photoluminescence (PL) spectrophotometry. From XRD, the average crystallite sizes of AP and APB are 39.1 and 46 nm, respectively, with a homogeneous morphology detected by SEM. UV and PL experiments showed that the compound is active under visible light, with an improvement in the lifetimes of the electrons and the holes in the presence of BaO with Ag3PO4. The as-synthesized APB photocatalyst sample showed a remarkably high degradation efficiency of MB (20 ppm, 50 mL) of around 94%, with a hydrogen production yield of around 7538 μmol/(h·g), after 120 min of illumination, which is greater than the degradation efficiency of the AP photocatalyst sample, which was about 88%. The high photodegradation efficiency was attributed to the electronic promotion effect of the BaO particles. The APB composite demonstrated an increased photocatalytic performance in effectively degrading an organic dye (MB) with no secondary pollutants when exposed to visible light irradiation. Full article
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14 pages, 3770 KiB  
Article
Hydrogen Production through Oxidative Steam Reforming of Acetic Acid over Ni Catalysts Supported on Ceria-Based Materials
by Pedro J. Megía, Anabel Morales, Arturo J. Vizcaíno, José A. Calles and Alicia Carrero
Catalysts 2022, 12(12), 1526; https://doi.org/10.3390/catal12121526 - 27 Nov 2022
Cited by 6 | Viewed by 1527
Abstract
Oxidative steam reforming allows higher energy efficiency and lowers coke deposition compared to traditional steam reforming. In this work, CeO2-based supports have been prepared with Ni as the active phase, and they were tested in the oxidative steam reforming of acetic [...] Read more.
Oxidative steam reforming allows higher energy efficiency and lowers coke deposition compared to traditional steam reforming. In this work, CeO2-based supports have been prepared with Ni as the active phase, and they were tested in the oxidative steam reforming of acetic acid. The influence of the O2/AcOH molar ratio (0–0.3) has been evaluated over Ni/CeO2. The results stated that by increasing oxygen content in the feeding mixture, acetic acid conversion increases, too, with a decrease in coke deposition and hydrogen yield. To have a proper balance between the acetic acid conversion and the hydrogen yield, an O2/AcOH molar ratio of 0.075 was selected to study the catalytic performance of Ni catalysts over different supports: commercial CeO2, a novel mesostructured CeO2, and CeO2-SBA-15. Due to higher Ni dispersion over the support, the mesostructured catalysts allowed higher acetic acid conversion and hydrogen yield compared to the nonporous Ni/CeO2. The best catalytic performance and the lowest coke formation (120.6 mgcoke·gcat−1·h−1) were obtained with the mesostructured Ni/CeO2. This sample reached almost complete conversion (>97%) at 500 °C, maintaining the hydrogen yield over 51.5% after 5 h TOS, being close to the predicted value by the thermodynamic equilibrium that is due to the synergistic coordination between Ni and CeO2 particles. Full article
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39 pages, 21138 KiB  
Article
Hydrogen Production through Bi-Reforming of Methane: Improving Ni Catalyst Performance via an Exsolution Approach
by Ekaterina Matus, Olga Sukhova, Mikhail Kerzhentsev, Ilyas Ismagilov, Svetlana Yashnik, Vladimir Ushakov, Olga Stonkus, Evgeny Gerasimov, Andrey Nikitin, Pankaj Bharali and Zinfer Ismagilov
Catalysts 2022, 12(12), 1493; https://doi.org/10.3390/catal12121493 - 22 Nov 2022
Cited by 9 | Viewed by 2309
Abstract
Hydrogen production through the bi-reforming of methane over exsolution-derived Ni catalysts has been studied. Nickel-based catalysts were prepared through the activation of (CeM)1−xNixOy (M = Al, La, Mg) solid solutions in a reducing gaseous medium. Their performance and [...] Read more.
Hydrogen production through the bi-reforming of methane over exsolution-derived Ni catalysts has been studied. Nickel-based catalysts were prepared through the activation of (CeM)1−xNixOy (M = Al, La, Mg) solid solutions in a reducing gaseous medium. Their performance and resistance to coking under the reaction conditions were controlled by regulating their textural, structural, morphological, and redox properties through adjustments to the composition of the oxide matrix (M/Ce = 0–4; x = 0.2–0.8; y = 1.0–2.0). The role of the M-dopant type in the genesis and properties of the catalysts was established. The efficiency of the catalysts in the bi-reforming of methane increased in the following series of M: M-free < La < Al < Mg, correlating with the structural behavior of the nickel active component and the anti-coking properties of the support matrix. The preferred M-type and M/Ce ratio determined the best performance of (CeM)1−xNixOy catalysts. At 800 °C the optimum Ce0.6Mg0.2Ni0.2O1.6 catalyst provided a stable H2 yield of 90% at a high level of CO2 and CH4 conversions (>85%). Full article
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14 pages, 3779 KiB  
Article
Clean Syngas and Hydrogen Co-Production by Gasification and Chemical Looping Hydrogen Process Using MgO-Doped Fe2O3 as Redox Material
by Maria Paola Bracciale, Martina Damizia, Paolo De Filippis and Benedetta de Caprariis
Catalysts 2022, 12(10), 1273; https://doi.org/10.3390/catal12101273 - 19 Oct 2022
Cited by 6 | Viewed by 1975
Abstract
Gasification converts biomass into syngas; however, severe cleaning processes are necessary due to the presence of tars, particulates and contaminants. The aim of this work is to propose a cleaning method system based on tar physical adsorption coupled with the production of pure [...] Read more.
Gasification converts biomass into syngas; however, severe cleaning processes are necessary due to the presence of tars, particulates and contaminants. The aim of this work is to propose a cleaning method system based on tar physical adsorption coupled with the production of pure H2 via a chemical looping process. Three fixed-bed reactors with a double-layer bed (NiO/Al2O3 and Fe-based particles) working in three different steps were used. First, NiO/Al2O3 is used to adsorb tar from syngas (300 °C); then, the adsorbed tar undergoes partial oxidization by NiO/Al2O3 to produce CO and H2 used for iron oxide reduction. In the third step, the reduced iron is oxidized with steam to produce pure H2 and to restore iron oxides. A double-layer fixed-bed reactor was fed alternatively by guaiacol and as tar model compounds, air and water were used. High-thermal-stability particles 60 wt% Fe2O3/40 wt% MgO synthetized by the coprecipitation method were used as Fe-based particles in six cycle tests. The adsorption efficiency of the NiO/Al2O3 bed is 98% and the gas phase formed is able to partially reduce iron, favoring the reduction kinetics. The efficiency of the process related to the H2 production after the first cycle is 35% and the amount of CO is less than 10 ppm. Full article
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11 pages, 3180 KiB  
Article
Visible Light-Responsive CeO2/MoS2 Composite for Photocatalytic Hydrogen Production
by Anuja A. Yadav, Yuvaraj M. Hunge and Seok-Won Kang
Catalysts 2022, 12(10), 1185; https://doi.org/10.3390/catal12101185 - 7 Oct 2022
Cited by 28 | Viewed by 3191
Abstract
Semiconductor-based photocatalyst materials play an important role in solar hydrogen production. In the present work, we achieved the successful synthesis of a CeO2/MoS2 composite using a facile hydrothermal method. For the preparation of the CeO2/MoS2 composite, the [...] Read more.
Semiconductor-based photocatalyst materials play an important role in solar hydrogen production. In the present work, we achieved the successful synthesis of a CeO2/MoS2 composite using a facile hydrothermal method. For the preparation of the CeO2/MoS2 composite, the hydrothermal process was carried out at a temperature of 120 °C for 24 h, and its performance in hydrogen production was tested. The CeO2/MoS2 composite was characterized using XRD, XPS, Raman spectroscopy, SEM, and optical investigation. The optical study showed that after forming a composite with MoS2, the absorption edge of CeO2 is shifted from the ultraviolet to the visible light region. Bandgap values decreased from 2.93 for CeO2 to 2.34 eV for the CeO2/MoS2 composite. In photocatalytic hydrogen production, Na2SO3–Na2S was used as a sacrificial agent. The CeO2/MoS2 composite exhibited superior photocatalytic hydrogen production performance compared to CeO2 and MoS2. The CeO2/MoS2 composite achieved higher charge separation efficiency, faster charge transfer, more active sites available for redox reactions, and greater affinity towards the reactant ions due to such properties its hydrogen evolution rate has reached 112.5 μmol/h. The photostability of the CeO2/MoS2 composite was tested in up to four cycles, with each cycle being four hours. Full article
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12 pages, 3241 KiB  
Article
Cu2O/CuS/ZnS Nanocomposite Boosts Blue LED-Light-Driven Photocatalytic Hydrogen Evolution
by Yu-Cheng Chang, Yung-Chang Chiao and Ya-Xiu Fun
Catalysts 2022, 12(9), 1035; https://doi.org/10.3390/catal12091035 - 11 Sep 2022
Cited by 15 | Viewed by 2488
Abstract
In the present work, we described the synthesis and characterization of the ternary Cu2O/CuS/ZnS nanocomposite using a facile two-step wet chemical method for blue LED-light-induced photocatalytic hydrogen production. The concentrations of the ZnS precursor and reaction time were essential in controlling [...] Read more.
In the present work, we described the synthesis and characterization of the ternary Cu2O/CuS/ZnS nanocomposite using a facile two-step wet chemical method for blue LED-light-induced photocatalytic hydrogen production. The concentrations of the ZnS precursor and reaction time were essential in controlling the photocatalytic hydrogen production efficiency of the Cu2O/CuS/ZnS nanocomposite under blue LED light irradiation. The optimized Cu2O/CuS/ZnS nanocomposite exhibited a maximum photocatalytic hydrogen evolution rate of 1109 µmolh−1g−1, which was remarkably higher than Cu2O nanostructures. Through the cycle stability it can be observed that the hydrogen production rate of the Cu2O/CuS/ZnS nanocomposite decreased after 4 cycles (1 cycle = 3 h), but it remained at 82.2% of the initial performance under blue LED light irradiation. These reasons are mainly attributed to the introduction of CuS and ZnS to construct a rationally coupled reaction system, which enables the synergistic utilization of photogenerated carriers and the increased absorption of visible light for boosting blue LED-light-driven photocatalytic hydrogen evolution. Full article
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Review

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21 pages, 2078 KiB  
Review
A Recent Review of Primary Hydrogen Carriers, Hydrogen Production Methods, and Applications
by Risheng Li and Hajime Kawanami
Catalysts 2023, 13(3), 562; https://doi.org/10.3390/catal13030562 - 10 Mar 2023
Cited by 11 | Viewed by 3107
Abstract
Hydrogen is a promising energy carrier, especially for transportation, owing to its unique physical and chemical properties. Moreover, the combustion of hydrogen gas generates only pure water; thus, its wide utilization can positively affect human society to achieve global net zero CO2 [...] Read more.
Hydrogen is a promising energy carrier, especially for transportation, owing to its unique physical and chemical properties. Moreover, the combustion of hydrogen gas generates only pure water; thus, its wide utilization can positively affect human society to achieve global net zero CO2 emissions by 2050. This review summarizes the characteristics of the primary hydrogen carriers, such as water, methane, methanol, ammonia, and formic acid, and their corresponding hydrogen production methods. Additionally, state-of-the-art studies and hydrogen energy applications in recent years are also included in this review. In addition, in the conclusion section, we summarize the advantages and disadvantages of hydrogen carriers and hydrogen production techniques and suggest the challenging tasks for future research. Full article
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38 pages, 4354 KiB  
Review
A Review of Coal and Biomass Hydrogasification: Process Layouts, Hydrogasifiers, and Catalysts
by Emilia Saraceno, Concetta Ruocco and Vincenzo Palma
Catalysts 2023, 13(2), 417; https://doi.org/10.3390/catal13020417 - 15 Feb 2023
Cited by 7 | Viewed by 2325
Abstract
Despite the increasing need for chemicals and energy, the scenario in which fossil feedstocks can be completely replaced by renewables is currently unrealistic. Thus, the combination of biomass and non-renewable matrix-based (i.e., coal) technologies could provide a greener way toward the partial substitution [...] Read more.
Despite the increasing need for chemicals and energy, the scenario in which fossil feedstocks can be completely replaced by renewables is currently unrealistic. Thus, the combination of biomass and non-renewable matrix-based (i.e., coal) technologies could provide a greener way toward the partial substitution of traditional fuels. The hydrogasification of carbonaceous feedstocks (coal and biomass) for the main production of CH4 offers a promising alternative to this end. However, hydrogasification has received very little attention, and the present review seeks to shed light on the process, reactor, and catalytic advances in the field. Independent of the selected matrices, various efforts have been devoted to the identification of efficient methods for the production of hydrogen feed to the gasifier and energy as well as the reduction in pollutant emissions from the plants. Moreover, the reactor configurations proposed are focused on the intensification of gas-solid contact to reduce by-product formation. The co-hydrogasification of both renewable and non-renewable feedstock is also reviewed, paying attention to the synergistic effect between the two matrices. In addition, due to the slow rates of hydrogasification reaction, the key role of catalysts and feedstock impurities on the reaction kinetics is discussed. Full article
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