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

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

Deadline for manuscript submissions: closed (30 April 2021) | Viewed by 71373

Printed Edition Available!
A printed edition of this Special Issue is available here.

Special Issue Editors

Dr. Marco Martino

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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
Dr. Concetta Ruocco

E-Mail Website
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

Special Issue Information

Dear Colleagues,

In the last decades, the production of hydrogen has taken on a strategic role in energy transition and in the mobility of the future. On September 18th last year, the European Union’s Energy Ministers signed a policy document to support the development of sustainable hydrogen, the “Hydrogen Initiative”, with the aim of seizing the opportunities offered by hydrogen technology in the view of a carbon-free economy and to guarantee the safe and sustainable production of energy for the European Union. Hydrogen is the ideal energy vector: thanks to its energy value, it is considered the best alternative to the use of gasoline in automotive applications and, in the future, it could be used to provide power for our homes and offices. Hydrogen can be obtained from renewable or fossil sources and a wide variety of processes are involved in H2 production, such as reforming, partial oxidation, electrolysis, catalytic decomposition, and microbiological processes. The present Special Issue is devoted to recent developments in the preparation of catalysts and their applications in hydrogen production processes. This Special Issue welcomes research papers, short communications, and review papers related to innovative catalytic formulations and configurations, as well as process integrations.

Dr. Marco Martino
Dr. Concetta Ruocco
Guest Editors

Manuscript Submission Information

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Keywords

  • hydrogen and biohydrogen production processes
  • process integration
  • new catalytic formulations and configurations
  • sustainability and renewables
  • low carbon technologies

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Related Special Issue

Published Papers (10 papers)

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Editorial

Jump to: Research, Review

3 pages, 184 KiB  
Editorial
Catalysts for Sustainable Hydrogen Production: Preparation, Applications and Process Integration
by Concetta Ruocco and Marco Martino
Catalysts 2022, 12(3), 322; https://doi.org/10.3390/catal12030322 - 11 Mar 2022
Cited by 4 | Viewed by 1955
Abstract
The earth is experiencing a series of epochal emergencies, directly related to the overexploitation of natural resources [...] Full article
(This article belongs to the Special Issue Catalysts for Sustainable Hydrogen Production: Preparation, Applications and Process Integration)

Research

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9 pages, 1960 KiB  
Article
Enhanced Electrocatalytic Activity of Stainless Steel Substrate by Nickel Sulfides for Efficient Hydrogen Evolution
by Jong-Sang Youn, Sangmin Jeong, Inhwan Oh, Sunyoung Park, Hien Duy Mai and Ki-Joon Jeon
Catalysts 2020, 10(11), 1274; https://doi.org/10.3390/catal10111274 - 3 Nov 2020
Cited by 15 | Viewed by 3013
Abstract
Water splitting is one of the efficient ways to produce hydrogen with zero carbon dioxide emission. Thus far, Pt has been regarded as a highly reactive catalyst for the hydrogen evolution reaction (HER); however, the high cost and rarity of Pt significantly hinder [...] Read more.
Water splitting is one of the efficient ways to produce hydrogen with zero carbon dioxide emission. Thus far, Pt has been regarded as a highly reactive catalyst for the hydrogen evolution reaction (HER); however, the high cost and rarity of Pt significantly hinder its commercial use. Herein, we successfully developed an HER catalyst composed of NiSx (x = 1 or 2) on stainless steel (NiSx/SUS) using electrodeposition and sulfurization techniques. Notably, the electrochemical active surface area(ECSA) of NiSx/SUS was improved more than two orders of magnitude, resulting in a considerable improvement in the electrochemical charge transfer and HER activity in comparison with stainless steel (SUS). The long-term HER examination by linear scan voltammetry (LSV) confirmed that NiSx/SUS was stable up to 2000 cycles. Full article
(This article belongs to the Special Issue Catalysts for Sustainable Hydrogen Production: Preparation, Applications and Process Integration)
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16 pages, 4873 KiB  
Article
Pt/Re/CeO2 Based Catalysts for CO-Water–Gas Shift Reaction: from Powders to Structured Catalyst
by Vincenzo Palma, Fausto Gallucci, Pluton Pullumbi, Concetta Ruocco, Eugenio Meloni and Marco Martino
Catalysts 2020, 10(5), 564; https://doi.org/10.3390/catal10050564 - 19 May 2020
Cited by 13 | Viewed by 3440
Abstract
This work focuses on the development of a Pt/Re/CeO2-based structured catalyst for a single stage water–gas shift process. In the first part of the work, the activity in water–gas shift reactions was evaluated for three Pt/Re/CeO2-based powder catalysts, with [...] Read more.
This work focuses on the development of a Pt/Re/CeO2-based structured catalyst for a single stage water–gas shift process. In the first part of the work, the activity in water–gas shift reactions was evaluated for three Pt/Re/CeO2-based powder catalysts, with Pt/Re ratio equal to 1/1, 1/2 ad 2/1 and total loading ≈ 1 wt%. The catalysts were prepared by sequential dry impregnation of commercial ceria, with the salts precursors of rhenium and platinum; the activity tests were carried out by feeding a reacting mixture with a variable CO/H2O ratio, equal to 7/14, 7/20 and 7/24, and the kinetic parameters were determined. The model which better described the experimental results involves the water–gas shift (WGS) reaction and CO as well as CO2 methanation. The preliminary tests showed that the catalyst with the Pt/Re ratio equal to 2/1 had the best performance, and this was selected for further investigations. In the second part of the work, a structured catalyst, obtained by coating a commercial aluminum alloy foam with the chosen catalytic formulation, was prepared and tested in different reaction conditions. The results demonstrated that a single stage water–gas shift process is achievable, obtaining a hydrogen production rate of 18.7 mmol/min at 685 K, at τ = 53 ms, by feeding a simulated reformate gas mixture (37.61 vol% H2, 9.31 vol% CO2, 9.31 vol% CO, 42.19 vol% H2O, 1.37 vol% CH4). Full article
(This article belongs to the Special Issue Catalysts for Sustainable Hydrogen Production: Preparation, Applications and Process Integration)
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20 pages, 2558 KiB  
Article
Kinetics of the Catalytic Thermal Degradation of Sugarcane Residual Biomass Over Rh-Pt/CeO2-SiO2 for Syngas Production
by Eliana Quiroga, Julia Moltó, Juan A. Conesa, Manuel F. Valero and Martha Cobo
Catalysts 2020, 10(5), 508; https://doi.org/10.3390/catal10050508 - 6 May 2020
Cited by 18 | Viewed by 3450
Abstract
Thermochemical processes for biomass conversion are promising to produce renewable hydrogen-rich syngas. In the present study, model fitting methods were used to propose thermal degradation kinetics during catalytic and non-catalytic pyrolysis (in N2) and combustion (in synthetic air) of sugarcane residual [...] Read more.
Thermochemical processes for biomass conversion are promising to produce renewable hydrogen-rich syngas. In the present study, model fitting methods were used to propose thermal degradation kinetics during catalytic and non-catalytic pyrolysis (in N2) and combustion (in synthetic air) of sugarcane residual biomass. Catalytic processes were performed over a Rh-Pt/CeO2-SiO2 catalyst and the models were proposed based on the Thermogravimetric (TG) analysis, TG coupled to Fourier Transformed Infrared Spectrometry (TG-FTIR) and TG coupled to mass spectrometry (TG-MS). Results showed three different degradation stages and a catalyst effect on product distribution. In pyrolysis, Rh-Pt/CeO2-SiO2 catalyst promoted reforming reactions which increased the presence of H2. Meanwhile, during catalytic combustion, oxidation of the carbon and hydrogen present in biomass favored the release of H2O, CO and CO2. Furthermore, the catalyst decreased the overall activation energies of pyrolysis and combustion from 120.9 and 154.9 kJ mol−1 to 107.0 and 138.0 kJ mol−1, respectively. Considering the positive effect of the Rh-Pt/CeO2-SiO2 catalyst during pyrolysis of sugarcane residual biomass, it could be considered as a potential catalyst to improve the thermal degradation of biomass for syngas production. Moreover, the proposed kinetic parameters are useful to design an appropriate thermochemical unit for H2-rich syngas production as a non-conventional energy technology. Full article
(This article belongs to the Special Issue Catalysts for Sustainable Hydrogen Production: Preparation, Applications and Process Integration)
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19 pages, 4239 KiB  
Article
Hydrogen Production from Steam Reforming of Acetic Acid as a Model Compound of the Aqueous Fraction of Microalgae HTL Using Co-M/SBA-15 (M: Cu, Ag, Ce, Cr) Catalysts
by Pedro J. Megía, Alicia Carrero, José A. Calles and Arturo J. Vizcaíno
Catalysts 2019, 9(12), 1013; https://doi.org/10.3390/catal9121013 - 2 Dec 2019
Cited by 21 | Viewed by 3721
Abstract
Hydrogen production derived from thermochemical processing of biomass is becoming an interesting alternative to conventional routes using fossil fuels. In this sense, steam reforming of the aqueous fraction of microalgae hydrothermal liquefaction (HTL) is a promising option for renewable hydrogen production. Since the [...] Read more.
Hydrogen production derived from thermochemical processing of biomass is becoming an interesting alternative to conventional routes using fossil fuels. In this sense, steam reforming of the aqueous fraction of microalgae hydrothermal liquefaction (HTL) is a promising option for renewable hydrogen production. Since the HTL aqueous fraction is a complex mixture, acetic acid has been chosen as model compound. This work studies the modification of Co/SBA-15 catalyst incorporating a second metal leading to Co-M/SBA-15 (M: Cu, Ag, Ce and Cr). All catalysts were characterized by N2 physisorption, ICP-AES, XRD, TEM, H2-TPR, H2-TPD and Raman spectroscopy. The characterization results evidenced that Cu and Ag incorporation decreased the cobalt oxides reduction temperatures, while Cr addition led to smaller Co0 crystallites better dispersed on the support. Catalytic tests done at 600 °C, showed that Co-Cr/SBA-15 sample gave hydrogen selectivity values above 70 mol % with a significant reduction in coke deposition. Full article
(This article belongs to the Special Issue Catalysts for Sustainable Hydrogen Production: Preparation, Applications and Process Integration)
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25 pages, 2343 KiB  
Article
Single and Dual Metal Oxides as Promising Supports for Carbon Monoxide Removal from an Actual Syngas: The Crucial Role of Support on the Selectivity of the Au–Cu System
by Bernay Cifuentes, Felipe Bustamante and Martha Cobo
Catalysts 2019, 9(10), 852; https://doi.org/10.3390/catal9100852 - 13 Oct 2019
Cited by 10 | Viewed by 5222
Abstract
A catalytic screening was performed to determine the effect of the support on the performance of an Au–Cu based system for the removal of CO from an actual syngas. First, a syngas was obtained from reforming of ethanol. Then, the reformer outlet was [...] Read more.
A catalytic screening was performed to determine the effect of the support on the performance of an Au–Cu based system for the removal of CO from an actual syngas. First, a syngas was obtained from reforming of ethanol. Then, the reformer outlet was connected to a second reactor, where Au–Cu catalysts supported on several single and dual metal oxides (i.e., CeO2, SiO2, ZrO2, Al2O3, La2O3, Fe2O3, CeO2-SiO2, CeO2-ZrO2, and CeO2-Al2O3) were evaluated. AuCu/CeO2 was the most active catalyst due to an elevated oxygen mobility over the surface, promoting CO2 formation from adsorption of C–O* and OH− intermediates on Au0 and CuO species. However, its lower capacity to release the surface oxygen contributes to the generation of stable carbon deposits, which lead to its rapid deactivation. On the other hand, AuCu/CeO2-SiO2 was more stable due to its high surface area and lower formation of formate and carbonate intermediates, mitigating carbon deposits. Therefore, use of dual supports could be a promising strategy to overcome the low stability of AuCu/CeO2. The results of this research are a contribution to integrated production and purification of H2 in a compact system. Full article
(This article belongs to the Special Issue Catalysts for Sustainable Hydrogen Production: Preparation, Applications and Process Integration)
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Review

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31 pages, 3760 KiB  
Review
Main Hydrogen Production Processes: An Overview
by Marco Martino, Concetta Ruocco, Eugenio Meloni, Pluton Pullumbi and Vincenzo Palma
Catalysts 2021, 11(5), 547; https://doi.org/10.3390/catal11050547 - 25 Apr 2021
Cited by 97 | Viewed by 12573
Abstract
Due to its characteristics, hydrogen is considered the energy carrier of the future. Its use as a fuel generates reduced pollution, as if burned it almost exclusively produces water vapor. Hydrogen can be produced from numerous sources, both of fossil and renewable origin, [...] Read more.
Due to its characteristics, hydrogen is considered the energy carrier of the future. Its use as a fuel generates reduced pollution, as if burned it almost exclusively produces water vapor. Hydrogen can be produced from numerous sources, both of fossil and renewable origin, and with as many production processes, which can use renewable or non-renewable energy sources. To achieve carbon neutrality, the sources must necessarily be renewable, and the production processes themselves must use renewable energy sources. In this review article the main characteristics of the most used hydrogen production methods are summarized, mainly focusing on renewable feedstocks, furthermore a series of relevant articles published in the last year, are reviewed. The production methods are grouped according to the type of energy they use; and at the end of each section the strengths and limitations of the processes are highlighted. The conclusions compare the main characteristics of the production processes studied and contextualize their possible use. Full article
(This article belongs to the Special Issue Catalysts for Sustainable Hydrogen Production: Preparation, Applications and Process Integration)
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17 pages, 10272 KiB  
Review
A Review of Hydrogen Purification Technologies for Fuel Cell Vehicles
by Zhemin Du, Congmin Liu, Junxiang Zhai, Xiuying Guo, Yalin Xiong, Wei Su and Guangli He
Catalysts 2021, 11(3), 393; https://doi.org/10.3390/catal11030393 - 19 Mar 2021
Cited by 170 | Viewed by 22203
Abstract
Nowadays, we face a series of global challenges, including the growing depletion of fossil energy, environmental pollution, and global warming. The replacement of coal, petroleum, and natural gas by secondary energy resources is vital for sustainable development. Hydrogen (H2) energy is [...] Read more.
Nowadays, we face a series of global challenges, including the growing depletion of fossil energy, environmental pollution, and global warming. The replacement of coal, petroleum, and natural gas by secondary energy resources is vital for sustainable development. Hydrogen (H2) energy is considered the ultimate energy in the 21st century because of its diverse sources, cleanliness, low carbon emission, flexibility, and high efficiency. H2 fuel cell vehicles are commonly the end-point application of H2 energy. Owing to their zero carbon emission, they are gradually replacing traditional vehicles powered by fossil fuel. As the H2 fuel cell vehicle industry rapidly develops, H2 fuel supply, especially H2 quality, attracts increasing attention. Compared with H2 for industrial use, the H2 purity requirements for fuel cells are not high. Still, the impurity content is strictly controlled since even a low amount of some impurities may irreversibly damage fuel cells’ performance and running life. This paper reviews different versions of current standards concerning H2 for fuel cell vehicles in China and abroad. Furthermore, we analyze the causes and developing trends for the changes in these standards in detail. On the other hand, according to characteristics of H2 for fuel cell vehicles, standard H2 purification technologies, such as pressure swing adsorption (PSA), membrane separation and metal hydride separation, were analyzed, and the latest research progress was reviewed. Full article
(This article belongs to the Special Issue Catalysts for Sustainable Hydrogen Production: Preparation, Applications and Process Integration)
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34 pages, 8026 KiB  
Review
Recent Advances in Noble Metal Catalysts for Hydrogen Production from Ammonia Borane
by Mengmeng Liu, Liu Zhou, Xianjin Luo, Chao Wan and Lixin Xu
Catalysts 2020, 10(7), 788; https://doi.org/10.3390/catal10070788 - 15 Jul 2020
Cited by 64 | Viewed by 8771
Abstract
Interest in chemical hydrogen storage has increased, because the supply of fossil fuels are limited and the harmful effects of burning fossil fuels on the environment have become a focus of public concern. Hydrogen, as one of the energy carriers, is useful for [...] Read more.
Interest in chemical hydrogen storage has increased, because the supply of fossil fuels are limited and the harmful effects of burning fossil fuels on the environment have become a focus of public concern. Hydrogen, as one of the energy carriers, is useful for the sustainable development. However, it is widely known that controlled storage and release of hydrogen are the biggest barriers in large-scale application of hydrogen energy. Ammonia borane (NH3BH3, AB) is deemed as one of the most promising hydrogen storage candidates on account of its high hydrogen to mass ratio and environmental benignity. Development of efficient catalysts to further improve the properties of chemical kinetics in the dehydrogenation of AB under appropriate conditions is of importance for the practical application of this system. In previous studies, a variety of noble metal catalysts and their supported metal catalysts (Pt, Pd, Au, Rh, etc.) have presented great properties in decomposing the chemical hydride to generate hydrogen, thus, promoting their application in dehydrogenation of AB is urgent. We analyzed the hydrolysis of AB from the mechanism of hydrogen release reaction to understand more deeply. Based on these characteristics, we aimed to summarize recent advances in the development of noble metal catalysts, which had excellent activity and stability for AB dehydrogenation, with prospect towards realization of efficient noble metal catalysts. Full article
(This article belongs to the Special Issue Catalysts for Sustainable Hydrogen Production: Preparation, Applications and Process Integration)
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74 pages, 6329 KiB  
Review
Bioalcohol Reforming: An Overview of the Recent Advances for the Enhancement of Catalyst Stability
by Vincenzo Palma, Concetta Ruocco, Marta Cortese and Marco Martino
Catalysts 2020, 10(6), 665; https://doi.org/10.3390/catal10060665 - 12 Jun 2020
Cited by 44 | Viewed by 5239
Abstract
The growing demand for energy production highlights the shortage of traditional resources and the related environmental issues. The adoption of bioalcohols (i.e., alcohols produced from biomass or biological routes) is progressively becoming an interesting approach that is used to restrict the consumption of [...] Read more.
The growing demand for energy production highlights the shortage of traditional resources and the related environmental issues. The adoption of bioalcohols (i.e., alcohols produced from biomass or biological routes) is progressively becoming an interesting approach that is used to restrict the consumption of fossil fuels. Bioethanol, biomethanol, bioglycerol, and other bioalcohols (propanol and butanol) represent attractive feedstocks for catalytic reforming and production of hydrogen, which is considered the fuel of the future. Different processes are already available, including steam reforming, oxidative reforming, dry reforming, and aqueous-phase reforming. Achieving the desired hydrogen selectivity is one of the main challenges, due to the occurrence of side reactions that cause coke formation and catalyst deactivation. The aims of this review are related to the critical identification of the formation of carbon roots and the deactivation of catalysts in bioalcohol reforming reactions. Furthermore, attention is focused on the strategies used to improve the durability and stability of the catalysts, with particular attention paid to the innovative formulations developed over the last 5 years. Full article
(This article belongs to the Special Issue Catalysts for Sustainable Hydrogen Production: Preparation, Applications and Process Integration)
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