Catalytic Reforming and Hydrogen Production: From the Past to the Future

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

Deadline for manuscript submissions: closed (30 November 2024) | Viewed by 16222

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School of Environmental Engineering, Technical University of Crete, GR-73100 Chania, Greece
Interests: methane production; catalyst; synthesis gas; hydrogen production; steam reforming; WGS reaction
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Department of Chemical and Biological Engineering, University at Buffalo, The State University of New York, Buffalo, NY 14260, USA
Interests: heterogeneous catalysis; nanoparticle synthesis; surface science; catalysts; environmental processes
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Special Issue Information

Dear Colleagues,

The Special Issue is dedicated to the exploration of catalytic reforming and hydrogen production, delving into a journey starting in the past of these processes and ending in their future applications. The catalytic reforming of light hydrocarbons stands out as a prominent technique for generating valuable products like synthesis gas. Syngas, a crucial intermediary substance in the creation of hydrogen, ammonia, methanol, and synthetic hydrocarbon fuels, holds significant potential for fostering a cleaner, more sustainable energy environment. Furthermore, through advancements in catalyst development, reactor designs, and process optimization strategies, hydrogen has emerged as a pivotal player in the global energy shift towards a more efficient and sustainable hydrogen economy.

This Special Issue aims to showcase the most recent research findings in heterogeneous catalysis concerning catalytic reforming and hydrogen production, assuming a future where clean energy takes center stage. We invite submissions in the form of original research papers or reviews that reflect the state of the art of this research area. Topics of interest include, but are not limited to, the following:

  • Methane conversion.
  • Dry reforming.
  • CO2 methanation.
  • Hydrogen production processes.
  • Water–gas shift (WGS) reaction.
  • Production of syngas.
  • Fischer–Tropsch synthesis.
  • Fuel cells.

Dr. Georgios Bampos
Dr. Paraskevi Panagiotopoulou
Dr. Eleni A. Kyriakidou
Guest Editors

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Keywords

  • syngas
  • hydrogen production
  • steam reforming
  • CO2 methanation
  • water gas shift (WGS) reaction
  • fuels
  • clean energy
  • hydrocarbons to fuels
  • fuel cells

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Related Special Issue

Published Papers (11 papers)

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Editorial

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4 pages, 152 KiB  
Editorial
Catalytic Reforming and Hydrogen Production: From the Past to the Future
by Georgios Bampos, Paraskevi Panagiotopoulou and Eleni A. Kyriakidou
Catalysts 2025, 15(4), 332; https://doi.org/10.3390/catal15040332 - 31 Mar 2025
Viewed by 415
Abstract
Continuously increasing energy demands and the intense environmental pollution caused by the increasing global population and modern lifestyles have driven research interest toward finding alternative sustainable energy sources [...] Full article

Research

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16 pages, 3071 KiB  
Article
Effect of Calcination-Induced Oxidation on the Photocatalytic H2 Production Performance of Cubic Cu2O/CuO Composite Photocatalysts
by Chi-Jung Chang, Chun-Wen Kang and Arul Pundi
Catalysts 2024, 14(12), 926; https://doi.org/10.3390/catal14120926 - 16 Dec 2024
Viewed by 947
Abstract
This study explores the H2 production performance of CuO/Cu2O with different morphology (nanocubes) synthesized by different methods using different sacrificial reagent (lactic acid), compared with the other three reported CuO/Cu2O photocatalysts used for H2 production. A cubic [...] Read more.
This study explores the H2 production performance of CuO/Cu2O with different morphology (nanocubes) synthesized by different methods using different sacrificial reagent (lactic acid), compared with the other three reported CuO/Cu2O photocatalysts used for H2 production. A cubic Cu2O photocatalyst was prepared using a hydrothermal method. It was then calcined at a certain temperature to form a cubic Cu2O/CuO composite photocatalyst. XRD, TEM, and XPS spectra confirmed the successful synthesis of cubic Cu2O/CuO composite photocatalysts by calcination-induced oxidation at a certain temperature. As the calcination temperature increases, the crystal phase of the photocatalyst changes from Cu2O to Cu2O/CuO and then to CuO. The effects of calcination-induced oxidation on morphology, light absorption, the separation of photoexcited carriers, and the H2 production activity of photocatalysts were studied. EPR spectra were monitored to analyze the oxygen vacancies in different samples. Mott–Schottky and Tauc plots were utilized to establish the band structure of the composite photocatalyst. Cu2O/CuO is a type II photocatalyst with a heterogeneous structure that helps to improve electron–hole separation efficiency. The H2 production efficiency of Cu2O/CuO composite photocatalyst reaches 11,888 μmol h−1g−1, 1.6 times that of Cu2O. The formation of the Cu2O/CuO heterojunction leads to enhanced light absorption, charge separation, and hydrogen production activity. Full article
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11 pages, 3582 KiB  
Article
Hydrothermal Synthesis of La-MoS2 and Its Catalytic Activity for Improved Hydrogen Evolution Reaction
by Archana Chaudhary, Rais Ahmad Khan, Sultan Saad Almadhhi, Ali Alsulmi, Khursheed Ahmad and Tae Hwan Oh
Catalysts 2024, 14(12), 893; https://doi.org/10.3390/catal14120893 - 5 Dec 2024
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Abstract
Herein, we report the synthesis and characterization of lanthanum-doped MoS2 (La-MoS2) via a hydrothermal route. The synthesized La-MoS2 was characterized using powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) techniques. The band gap of La-MoS [...] Read more.
Herein, we report the synthesis and characterization of lanthanum-doped MoS2 (La-MoS2) via a hydrothermal route. The synthesized La-MoS2 was characterized using powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) techniques. The band gap of La-MoS2 was observed to be 1.68 eV, compared to 1.80 eV for synthesized MoS2. In the photoluminescence (PL) spectra, a decrease in the intensity was observed for La-MoS2 compared to MoS2, which suggests that due to doping with charged La3+, separation increases. The as-synthesized MoS2 and La-MoS2 were used for photocatalytic hydrogen evolution reactions (HERs), exhibiting 928 µmol·g−1 evolution of H2 in five hours for a 10 mg dose of La-MoS2, compared to 612 µmol·g−1 for MoS2. A 50 mg mass of the catalyst (La-MoS2) exhibited enhanced H2 production of 1670 µmol·g−1 after five hours. The higher rate of the HER for La-MoS2 is because of doping with La3+. The photocatalytic hydrogen evolution performance of La-MoS2 was also evaluated for different doses of La-MoS2 exhibiting reusability up to the fourth cycle, showing potential applications of La-MoS2 in hydrogen evolution reactions. Mechanistic aspects of the HER on the surface of La-MoS2 have also been discussed. Full article
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16 pages, 7807 KiB  
Article
Aqueous Phase Reforming by Platinum Catalysts: Effect of Particle Size and Carbon Support
by Xuan Trung Nguyen, Ella Kitching, Thomas Slater, Emanuela Pitzalis, Jonathan Filippi, Werner Oberhauser and Claudio Evangelisti
Catalysts 2024, 14(11), 798; https://doi.org/10.3390/catal14110798 - 7 Nov 2024
Viewed by 1612
Abstract
Aqueous phase reforming (APR) is a promising method for producing hydrogen from biomass-derived feedstocks. In this study, carbon-supported Pt catalysts containing particles of different sizes (below 3 nm) were deposited on different commercially available carbons (i.e., Vulcan XC72 and Ketjenblack EC-600JD) using the [...] Read more.
Aqueous phase reforming (APR) is a promising method for producing hydrogen from biomass-derived feedstocks. In this study, carbon-supported Pt catalysts containing particles of different sizes (below 3 nm) were deposited on different commercially available carbons (i.e., Vulcan XC72 and Ketjenblack EC-600JD) using the metal vapor synthesis approach, and their catalytic efficiency and stability were evaluated in the aqueous phase reforming of ethylene glycol, the simplest polyol containing both C–C and C–O bonds. High-surface-area carbon supports were found to stabilize Pt nanoparticles with a mean diameter of 1.5 nm, preventing metal sintering. In contrast, Pt single atoms and clusters (below 0.5 nm) were not stable under the reaction conditions, contributing minimally to catalytic activity and promoting particle growth. The most effective catalyst PtA/CK, containing a mean Pt NP size of 1.5 nm and highly dispersed on Ketjenblack carbon, demonstrated high hydrogen site time yield (8.92 min−1 at 220 °C) and high stability under both high-temperature treatment conditions and over several recycling runs. The catalyst was also successfully applied to the APR of polyethylene terephthalate (PET), showing potential for hydrogen production from plastic waste. Full article
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12 pages, 8618 KiB  
Article
Hydrogen and CO Over-Equilibria in Catalytic Reactions of Methane Reforming
by Vitaliy R. Trishch, Mykhailo O. Vilboi, Gregory S. Yablonsky and Dmytro O. Kovaliuk
Catalysts 2024, 14(11), 773; https://doi.org/10.3390/catal14110773 - 31 Oct 2024
Cited by 1 | Viewed by 938
Abstract
Hydrogen and carbon monoxide over-equilibria have been found computationally in kinetic dependencies of methane-reforming catalytic reactions (steam and dry reforming) using the conditions of the conservatively perturbed equilibrium (CPE) phenomenon, i.e., at the initial equilibrium concentration of hydrogen or carbon monoxide. The influence [...] Read more.
Hydrogen and carbon monoxide over-equilibria have been found computationally in kinetic dependencies of methane-reforming catalytic reactions (steam and dry reforming) using the conditions of the conservatively perturbed equilibrium (CPE) phenomenon, i.e., at the initial equilibrium concentration of hydrogen or carbon monoxide. The influence of the pressure, temperature, flow rate and composition of the initial mixture on the position of the CPE point (the extremum point) was investigated over a wide domain of parameters. The CPE phenomenon significantly increases the product concentration (H2 and CO) at the reactor length, which is significantly less than the reactor length required to reach equilibrium. The CPE point is interpreted as the “turning point” in kinetic behaviour. Recommendations on temperature and pressure regimes are different from the traditional ones related to Le Chatelier’s law. The obtained results provide valuable information on optimal reaction conditions for complex reversible chemical transformations, offering potential applications in chemical engineering processes. Full article
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18 pages, 4765 KiB  
Article
Kinetic Characterization of Pt/Al2O3 Catalyst for Hydrogen Production via Methanol Aqueous-Phase Reforming
by José Sousa, Paranjeet Lakhtaria, Paulo Ribeirinha, Werneri Huhtinen, Johan Tallgren and Adélio Mendes
Catalysts 2024, 14(10), 741; https://doi.org/10.3390/catal14100741 - 21 Oct 2024
Cited by 1 | Viewed by 1609
Abstract
Compared to steam reforming, methanol aqueous-phase reforming (APR) converts methanol to hydrogen and carbon dioxide at lower temperatures, but also displays lower conversion rates. Herein, methanol APR is studied over the active Pt/Al2O3 catalyst under different operating conditions. Studies were [...] Read more.
Compared to steam reforming, methanol aqueous-phase reforming (APR) converts methanol to hydrogen and carbon dioxide at lower temperatures, but also displays lower conversion rates. Herein, methanol APR is studied over the active Pt/Al2O3 catalyst under different operating conditions. Studies were conducted at different temperatures, pressures, methanol mass fractions, and residence times. APR performance was evaluated in terms of methanol conversion, hydrogen production rate, hydrogen selectivity, and by-product formation. The results revealed that an increase in operating pressure and methanol mass fraction had an adverse effect on the APR performance. Conversely, it was found that hydrogen selectivity was unaffected by the operating pressure and residence time for the methanol feed mass fraction of 5%. For the methanol feed mass fraction of 55%, hydrogen selectivity was improved by operating pressure and residence time. The alumina support phase change to boehmite as well as sintering and leaching of the catalytic particles were observed during catalyst stability experiments. Additionally, a comparison between methanol steam reforming (MSR) and APR was also performed. Full article
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20 pages, 5958 KiB  
Article
Dry Reforming of Methane (DRM) over Hydrotalcite-Based Ni-Ga/(Mg, Al)Ox Catalysts: Tailoring Ga Content for Improved Stability
by Ahmed Y. Elnour, Ahmed E. Abasaeed, Anis H. Fakeeha, Ahmed A. Ibrahim, Salwa B. Alreshaidan and Ahmed S. Al-Fatesh
Catalysts 2024, 14(10), 721; https://doi.org/10.3390/catal14100721 - 16 Oct 2024
Cited by 1 | Viewed by 1776
Abstract
Dry reforming of methane (DRM) is a promising way to convert methane and carbon dioxide into syngas, which can be further utilized to synthesize value-added chemicals. One of the main challenges for the DRM process is finding catalysts that are highly active and [...] Read more.
Dry reforming of methane (DRM) is a promising way to convert methane and carbon dioxide into syngas, which can be further utilized to synthesize value-added chemicals. One of the main challenges for the DRM process is finding catalysts that are highly active and stable. This study explores the potential use of Ni-based catalysts modified by Ga. Different Ni-Ga/(Mg, Al)Ox catalysts, with various Ga/Ni molar ratios (0, 0.1, 0.3, 0.5, and 1), were synthesized by the co-precipitation method. The catalysts were tested for the DRM reaction to evaluate their activity and stability. The Ni/(Mg, Al)Ox and its Ga-modified Ni-Ga/(Mg, Al)Ox were characterized by N2 adsorption–desorption, Fourier Transform Infrared Spectroscopy (FTIR), H2-temperature-programmed reduction (TPR), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and Raman techniques. The test of catalytic activity, at 700 °C, 1 atm, GHSV of 42,000 mL/h/g, and a CH4: CO2 ratio of 1, revealed that Ga incorporation effectively enhanced the catalyst stability. Particularly, the Ni-Ga/(Mg, Al)Ox catalyst with Ga/Ni ratio of 0.3 exhibited the best catalytic performance, with CH4 and CO2 conversions of 66% and 74%, respectively, and an H2/CO ratio of 0.92. Furthermore, the CH4 and CO2 conversions increased from 34% and 46%, respectively, when testing at 600 °C, to 94% and 96% when the catalytic activity was operated at 850 °C. The best catalyst’s 20 h stream performance demonstrated its great stability. DFT analysis revealed an alteration in the electronic properties of nickel upon Ga incorporation, the d-band center of the Ga modified catalyst (Ga/Ni ratio of 0.3) shifted closer to the Fermi level, and a charge transfer from Ga to Ni atoms was observed. This research provides valuable insights into the development of Ga-modified catalysts and emphasizes their potential for efficient conversion of greenhouse gases into syngas. Full article
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18 pages, 2811 KiB  
Article
Are Rh Catalysts a Suitable Choice for Bio-Oil Reforming? The Case of a Commercial Rh Catalyst in the Combined H2O and CO2 Reforming of Bio-Oil
by José Valecillos, Leire Landa, Gorka Elordi, Aingeru Remiro, Javier Bilbao and Ana Guadalupe Gayubo
Catalysts 2024, 14(9), 571; https://doi.org/10.3390/catal14090571 - 29 Aug 2024
Cited by 1 | Viewed by 1018
Abstract
Bio-oil combined steam/dry reforming (CSDR) with H2O and CO2 as reactants is an attractive route for the joint valorization of CO2 and biomass towards the sustainable production of syngas (H2 + CO). The technological development of the process [...] Read more.
Bio-oil combined steam/dry reforming (CSDR) with H2O and CO2 as reactants is an attractive route for the joint valorization of CO2 and biomass towards the sustainable production of syngas (H2 + CO). The technological development of the process requires the use of an active and stable catalyst, but also special attention should be paid to its regeneration capacity due to the unavoidable and quite rapid catalyst deactivation in the reforming of bio-oil. In this work, a commercial Rh/ZDC (zirconium-doped ceria) catalyst was tested for reaction–regeneration cycles in the bio-oil CSDR in a fluidized bed reactor, which is beneficial for attaining an isothermal operation and, moreover, minimizes catalyst deactivation by coke deposition compared to a fixed-bed reactor. The fresh, spent, and regenerated catalysts were characterized using either N2 physisorption, H2-TPR, TPO, SEM, TEM, or XRD. The Rh/ZDC catalyst is initially highly active for the syngas production (yield of 77% and H2/CO ratio of 1.2) and for valorizing CO2 (conversion of 22%) at 700 °C, with space time of 0.125 gcatalyst h (goxygenates)−1 and CO2/H2O/C ratio of 0.6/0.5/1. The catalyst activity evolves in different periods that evidence a selective deactivation of the catalyst for the reforming reactions of the different compounds, with the CH4 reforming reactions (with both steam and CO2) being more rapidly affected by catalyst deactivation than the reforming of hydrocarbons or oxygenates. After regeneration, the catalyst’s textural properties are not completely restored and there is a change in the Rh–support interaction that irreversibly deactivates the catalyst for the CH4 reforming reactions (both SR and DR). As a result, the coke formed over the regenerated catalyst is different from that over the fresh catalyst, being an amorphous mass (of probably turbostractic nature) that encapsulates the catalyst and causes rapid deactivation. Full article
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19 pages, 5418 KiB  
Article
Ni-Ag Catalysts for Hydrogen Production through Dry Reforming of Methane: Characterization and Performance Evaluation
by Hayat Henni, Rafik Benrabaa, Pascal Roussel and Axel Löfberg
Catalysts 2024, 14(7), 400; https://doi.org/10.3390/catal14070400 - 25 Jun 2024
Cited by 4 | Viewed by 1705
Abstract
To investigate the influence of Ag and the loading of Ni species, Ni-Ag type catalysts were synthesized with varying Ni/Ag ratios (1, 1.5 and 2) using the coprecipitation method. The catalysts were extensively characterized using various techniques such as TG-DSC-SM, XRD, ICP, BET, [...] Read more.
To investigate the influence of Ag and the loading of Ni species, Ni-Ag type catalysts were synthesized with varying Ni/Ag ratios (1, 1.5 and 2) using the coprecipitation method. The catalysts were extensively characterized using various techniques such as TG-DSC-SM, XRD, ICP, BET, SEM-EDX and TPR and subsequently tested in the CH4/CO2 reaction without any pretreatment. Regardless of the ratio employed, a phase mixture containing NiO and Ag was observed after calcination under air between 600 °C and 1200 °C. SEM analysis confirmed the presence of a close interface between Ag and NiO. The specific surface area was found to be significantly higher for the catalyst with lower Ni content (R = 1). TPR analysis demonstrated that the inclusion of Ag facilitated the reduction of Ni at lower temperatures. XRD analyses of the spent catalyst confirmed catalyst reduction during the reaction. Among the samples, a catalyst with Ni/Ag = 1 exhibited superior catalytic activity without any pretreatment under a reduction atmosphere, in which case the conversions of methane and CO2 at 650 °C amounted to 38 and 45 mol%, respectively, with H2/CO = 0.7 and 71 mol% of H2. The presence of Ag species enhances the stability of the Ni catalyst and improves catalytic performance in the dry reforming of methane. Full article
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Review

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37 pages, 5272 KiB  
Review
Review on Synthesis and Catalytic Properties of Cobalt Manganese Oxide Spinels (CoxMn3−xO4, 0 < x < 3)
by Kende Attila Béres, Zoltán Homonnay and László Kótai
Catalysts 2025, 15(1), 82; https://doi.org/10.3390/catal15010082 - 16 Jan 2025
Viewed by 1369
Abstract
The cobalt manganese oxides, especially the spinels and related (multiphase) materials described with the formula CoxMn3−xO4 (0 < x < 3), are widely used catalysts in a range of processes in significant industrial and environmental areas. The [...] Read more.
The cobalt manganese oxides, especially the spinels and related (multiphase) materials described with the formula CoxMn3−xO4 (0 < x < 3), are widely used catalysts in a range of processes in significant industrial and environmental areas. The great diversity in the phase relations, composition, and metal ion valences, together with ion and vacancy site distribution variations, results in great variety and activity as catalysts in various industrially important redox processes such as the removal of CO or volatile organic substances (VOCs) from the air and oxidative destruction of pollutants such as dyes and pharmaceuticals from wastewater using peroxides. These mixed oxides can gain application in the selective oxidation of organic molecules like 5-hydroxyfurfural or aromatic alcohols such as vanillyl alcohol or in the production of fuels and other valuable chemicals (alcohols, esters) with the Fischer–Tropsch method. In this review, we summarize these redox-based reactions in light of the chemical and phase composition of the catalysts with the formula CoxMn3−xO4 with 0 < x < 3. Full article
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35 pages, 4170 KiB  
Review
Recent Advances in Methanol Steam Reforming Catalysts for Hydrogen Production
by Mengyuan Zhang, Diru Liu, Yiying Wang, Lin Zhao, Guangyan Xu, Yunbo Yu and Hong He
Catalysts 2025, 15(1), 36; https://doi.org/10.3390/catal15010036 - 3 Jan 2025
Cited by 2 | Viewed by 2258
Abstract
The pursuit of carbon neutrality has accelerated advancements in sustainable hydrogen production and storage methods, increasing the importance of methanol steam reforming (MSR) technology. Catalysts are central to MSR technology and are primarily classified into copper-based and noble metal-based catalysts. This review begins [...] Read more.
The pursuit of carbon neutrality has accelerated advancements in sustainable hydrogen production and storage methods, increasing the importance of methanol steam reforming (MSR) technology. Catalysts are central to MSR technology and are primarily classified into copper-based and noble metal-based catalysts. This review begins with an examination of the active components of these catalysts, tracing the evolution of the understanding of active sites over the past four decades. It then explores the roles of various supports and promoters, along with mechanisms of catalyst deactivation. To address the diverse perspectives on the MSR reaction mechanism, the existing research is systematically organized and synthesized, providing a detailed account of the reaction mechanisms associated with both catalyst types. The discussion concludes with a forward-looking perspective on MSR catalyst development, emphasizing strategies such as anti-sintering methods for copper-based catalysts, approaches to reduce byproduct formation in palladium-based catalysts, comprehensive research methodologies for MSR mechanisms, and efforts to enhance atomic utilization efficiency. Full article
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