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Advanced Catalysis in Hydrogen Production from Formic Acid and Methanol
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Advanced Catalysis in Hydrogen Production from Formic Acid and Methanol

A special issue of Energies (ISSN 1996-1073). This special issue belongs to the section "A5: Hydrogen Energy".

Deadline for manuscript submissions: closed (31 March 2020) | Viewed by 28155

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

Special Issue Editor

Dr. Dmitri A. Bulushev

E-Mail Website
Guest Editor
Laboratory of Catalytic Methods of Solar Energy Transformation, Boreskov Institute of Catalysis, SB RAS, 630090 Novosibirsk, Russia
Interests: catalysis; nanomaterials; hydrogen production; biomass conversion
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear colleagues,

Studies of catalytic decomposition of formic acid and methanol have more than 100 years of history, contributing significantly to the science and applications of catalysis. These studies are related to the name of Paul Sabatier, who was awarded the Nobel Prize in Chemistry in 1912. Formic acid and methanol contain a sufficient amount of hydrogen that can be liberated at mild conditions using catalysis. Formic acid and methanol are considered as liquid organic hydrogen carriers (LOHCs) and can be produced using renewable methods from biomass or by CO2 hydrogenation. Therefore, the studies in this field recently have become focused on the development of efficient catalysts for hydrogen production from these compounds.

The aim of this Special Issue is to discuss the field of hydrogen production by the catalytic decomposition (or steam-reforming) of formic acid and methanol. The questions of preparation and characterization of efficient homogeneous or heterogeneous catalysts, reaction mechanism and kinetics, reactor systems engineering, and catalyst design could be discussed in this issue. We invite researchers to submit their theoretical and/or experimental original results.

Dr. Dmitri A. Bulushev
Guest Editor

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Keywords

  • hydrogen
  • formic acid
  • methanol
  • decomposition
  • steam reforming
  • supported catalysts
  • metal complexes

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Published Papers (7 papers)

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Research

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8 pages, 1485 KiB  
Article
The Role of Support in Formic Acid Decomposition on Gold Catalysts
by Vladimir Sobolev, Igor Asanov and Konstantin Koltunov
Energies 2019, 12(21), 4198; https://doi.org/10.3390/en12214198 - 4 Nov 2019
Cited by 9 | Viewed by 3569
Abstract
Formic acid (FA) can easily be decomposed, affording molecular hydrogen through a controllable catalytic process, thus attaining great importance as a convenient hydrogen carrier for hydrogen energetics. Supported gold nanoparticles are considered to be among the most promising catalysts for such applications. However, [...] Read more.
Formic acid (FA) can easily be decomposed, affording molecular hydrogen through a controllable catalytic process, thus attaining great importance as a convenient hydrogen carrier for hydrogen energetics. Supported gold nanoparticles are considered to be among the most promising catalysts for such applications. However, questions remain regarding the influence of the catalyst support on the reaction selectivity. In this study, we have examined the catalytic activity of typical gold catalysts, such as Au/TiO2, Au/SiO2, and Au/Al2O3 in decomposition of FA, and then compared it with the catalytic activity of corresponding supports. The performance of each catalyst and support was evaluated using a gas-flow packed-bed reactor. It is shown that the target reaction, FA → H2 + CO2, is provided by the presence of gold nanoparticles, whereas the concurrent, undesirable pathway, such as FA → H2O + CO, results exclusively from the acid-base behavior of supports. Full article
(This article belongs to the Special Issue Advanced Catalysis in Hydrogen Production from Formic Acid and Methanol)
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10 pages, 3040 KiB  
Article
Effects of the Carbon Support Doping with Nitrogen for the Hydrogen Production from Formic Acid over Ni Catalysts
by Alina D. Nishchakova, Dmitri A. Bulushev, Olga A. Stonkus, Igor P. Asanov, Arcady V. Ishchenko, Alexander V. Okotrub and Lyubov G. Bulusheva
Energies 2019, 12(21), 4111; https://doi.org/10.3390/en12214111 - 28 Oct 2019
Cited by 23 | Viewed by 3373
Abstract
Porous nitrogen-doped and nitrogen-free carbon materials possessing high specific surface areas (400–1000 m2 g−1) were used for deposition of Ni by impregnation with nickel acetate followed by reduction. The nitrogen-doped materials synthesized by decomposition of acetonitrile at 973, 1073, and [...] Read more.
Porous nitrogen-doped and nitrogen-free carbon materials possessing high specific surface areas (400–1000 m2 g−1) were used for deposition of Ni by impregnation with nickel acetate followed by reduction. The nitrogen-doped materials synthesized by decomposition of acetonitrile at 973, 1073, and 1173 K did not differ much in the total content of incorporated nitrogen (4–5 at%), but differed in the ratio of the chemical forms of nitrogen. An X-ray photoelectron spectroscopy study showed that the rise in the synthesis temperature led to a strong growth of the content of graphitic nitrogen on the support accompanied by a reduction of the content of pyrrolic nitrogen. The content of pyridinic nitrogen did not change significantly. The prepared nickel catalysts supported on nitrogen-doped carbons showed by a factor of up to two higher conversion of formic acid as compared to that of the nickel catalyst supported on the nitrogen-free carbon. This was related to stabilization of Ni in the state of single Ni2+ cations or a few atoms clusters by the pyridinic nitrogen sites. The nitrogen-doped nickel catalysts possessed a high stability in the reaction at least within 5 h and a high selectivity to hydrogen (97%). Full article
(This article belongs to the Special Issue Advanced Catalysis in Hydrogen Production from Formic Acid and Methanol)
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14 pages, 3941 KiB  
Article
Nitrogen Doped Carbon Nanotubes and Nanofibers for Green Hydrogen Production: Similarities in the Nature of Nitrogen Species, Metal–Nitrogen Interaction, and Catalytic Properties
by Olga Podyacheva, Alexander Lisitsyn, Lidiya Kibis, Andrei Boronin, Olga Stonkus, Vladimir Zaikovskii, Arina Suboch, Vladimir Sobolev and Valentin Parmon
Energies 2019, 12(20), 3976; https://doi.org/10.3390/en12203976 - 18 Oct 2019
Cited by 22 | Viewed by 2925
Abstract
The effect of nitrogen doped bamboo-like carbon nanotubes (N–CNTs) on the properties of supported platinum (0.2 and 1 wt %) catalysts in formic acid decomposition for hydrogen production was studied. It was shown that both impregnation and homogeneous precipitation routes led to the [...] Read more.
The effect of nitrogen doped bamboo-like carbon nanotubes (N–CNTs) on the properties of supported platinum (0.2 and 1 wt %) catalysts in formic acid decomposition for hydrogen production was studied. It was shown that both impregnation and homogeneous precipitation routes led to the formation of electron-deficient platinum stabilized by pyridinic nitrogen sites of the N–CNTs. The electron-deficient platinum species strongly enhanced the activity and selectivity of the Pt/N–CNTs catalysts when compared to the catalysts containing mainly metallic platinum nanoparticles. A comparison of bamboo-like N–CNTs and herring-bone nitrogen doped carbon nanofibers (N–CNFs) as the catalyst support allowed us to conclude that the catalytic properties of supported platinum are determined by its locally one-type interaction with pyridinic nitrogen sites of the N–CNTs or N–CNFs irrespective of substantial structural differences between nanotubes and nanofibers. Full article
(This article belongs to the Special Issue Advanced Catalysis in Hydrogen Production from Formic Acid and Methanol)
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13 pages, 4191 KiB  
Article
Boosting Hydrogen Production from Formic Acid over Pd Catalysts by Deposition of N-Containing Precursors on the Carbon Support
by Fedor S. Golub, Sergey Beloshapkin, Artem V. Gusel’nikov, Vasily A. Bolotov, Valentin N. Parmon and Dmitri A. Bulushev
Energies 2019, 12(20), 3885; https://doi.org/10.3390/en12203885 - 14 Oct 2019
Cited by 31 | Viewed by 4040
Abstract
Formic acid is a promising liquid organic hydrogen carrier (LOHC) since it has relatively high hydrogen content (4.4 wt%), low inflammability, low toxicity and can be obtained from biomass or from CO2. The aim of the present research was the creation [...] Read more.
Formic acid is a promising liquid organic hydrogen carrier (LOHC) since it has relatively high hydrogen content (4.4 wt%), low inflammability, low toxicity and can be obtained from biomass or from CO2. The aim of the present research was the creation of efficient 1 wt% Pd catalysts supported on mesoporous graphitic carbon (Sibunit) for the hydrogen production from gas-phase formic acid. For this purpose, the carbon support was modified by pyrolysis of deposited precursors containing pyridinic nitrogen such as melamine (Mel), 2,2′-bipyridine (Bpy) or 1,10-phenanthroline (Phen) at 673 K. The following activity trend of the catalysts Pd/Mel/C > Pd/C ~ Pd/Bpy/C > Pd/Phen/C was obtained. The activity of the Pd/Mel/C catalyst was by a factor of 4 higher than the activity of the Pd/C catalyst at about 373 K and the apparent activation energy was significantly lower than those for the other catalysts (32 vs. 42–46 kJ/mol). The high activity of the melamine-based samples was explained by a high dispersion of Pd nanoparticles (~2 nm, HRTEM) and their strong electron-deficient character (XPS) provided by interaction of Pd with pyridinic nitrogen species of the support. The presented results can be used for the development of supported Pd catalysts for hydrogen production from different liquid organic hydrogen carriers. Full article
(This article belongs to the Special Issue Advanced Catalysis in Hydrogen Production from Formic Acid and Methanol)
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10 pages, 1401 KiB  
Article
Production of Hydrogen-Rich Gas by Formic Acid Decomposition over CuO-CeO2/γ-Al2O3 Catalyst
by Alexey Pechenkin, Sukhe Badmaev, Vladimir Belyaev and Vladimir Sobyanin
Energies 2019, 12(18), 3577; https://doi.org/10.3390/en12183577 - 19 Sep 2019
Cited by 12 | Viewed by 3193
Abstract
Formic acid decomposition to H2-rich gas was investigated over a CuO-CeO2/γ-Al2O3 catalyst. The catalyst was characterized by XRD, HR TEM and EDX methods. A 100% conversion of formic acid was observed over the copper-ceria catalyst under [...] Read more.
Formic acid decomposition to H2-rich gas was investigated over a CuO-CeO2/γ-Al2O3 catalyst. The catalyst was characterized by XRD, HR TEM and EDX methods. A 100% conversion of formic acid was observed over the copper-ceria catalyst under ambient pressure, at 200–300 °C, N2:HCOOH = 75:25 vol.% and flow rate 3500–35,000 h−1 with H2 yield of 98%, wherein outlet CO concentration is below the equilibrium data (<0.5 vol.%). The copper-ceria catalyst proved to be promising for multifuel processor application, and the H2 generation from dimethoxymethane, methanol, dimethyl ether and formic acid on the same catalyst for fuel cell supply. Full article
(This article belongs to the Special Issue Advanced Catalysis in Hydrogen Production from Formic Acid and Methanol)
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Review

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25 pages, 6027 KiB  
Review
From Homogeneous to Heterogenized Molecular Catalysts for H2 Production by Formic Acid Dehydrogenation: Mechanistic Aspects, Role of Additives, and Co-Catalysts
by Panagiota Stathi, Maria Solakidou, Maria Louloudi and Yiannis Deligiannakis
Energies 2020, 13(3), 733; https://doi.org/10.3390/en13030733 - 7 Feb 2020
Cited by 31 | Viewed by 5313
Abstract
H2 production via dehydrogenation of formic acid (HCOOH, FA), sodium formate (HCOONa, SF), or their mixtures, at near-ambient conditions, T < 100 °C, P = 1 bar, is intensively pursued, in the context of the most economically and environmentally eligible technologies. Herein [...] Read more.
H2 production via dehydrogenation of formic acid (HCOOH, FA), sodium formate (HCOONa, SF), or their mixtures, at near-ambient conditions, T < 100 °C, P = 1 bar, is intensively pursued, in the context of the most economically and environmentally eligible technologies. Herein we discuss molecular catalysts (ML), consisting of a metal center (M, e.g., Ru, Ir, Fe, Co) and an appropriate ligand (L), which exemplify highly efficient Turnover Numbers (TONs) and Turnover Frequencies (TOFs) in H2 production from FA/SF. Typically, many of these ML catalysts require the presence of a cofactor that promotes their optimal cycling. Thus, we distinguish the concept of such cofactors in additives vs. co-catalysts: When used at high concentrations, that is stoichiometric amounts vs. the substrate (HCOONa, SF), the cofactors are sacrificial additives. In contrast, co-catalysts are used at much lower concentrations, that is at stoichiometric amount vs. the catalyst. The first part of the present review article discusses the mechanistic key steps and key controversies in the literature, taking into account theoretical modeling data. Then, in the second part, the role of additives and co-catalysts as well as the role of the solvent and the eventual inhibitory role of H2O are discussed in connection to the main mechanistic steps. For completeness, photons used as activators of ML catalysts are also discussed in the context of co-catalysts. In the third part, we discuss examples of promising hybrid nanocatalysts, consisting of a molecular catalyst ML attached on the surface of a nanoparticle. In the same context, we discuss nanoparticulate co-catalysts and hybrid co-catalysts, consisting of catalyst attached on the surface of a nanoparticle, and their role in the performance of molecular catalysts ML. Full article
(This article belongs to the Special Issue Advanced Catalysis in Hydrogen Production from Formic Acid and Methanol)
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27 pages, 7397 KiB  
Review
Hydrogen Production from Formic Acid Attained by Bimetallic Heterogeneous PdAg Catalytic Systems
by Miriam Navlani-García, David Salinas-Torres and Diego Cazorla-Amorós
Energies 2019, 12(21), 4027; https://doi.org/10.3390/en12214027 - 23 Oct 2019
Cited by 29 | Viewed by 4706
Abstract
The production of H2 from the so-called Liquid Organic Hydrogen Carriers (LOHC) has recently received great focus as an auspicious option to conventional hydrogen storage technologies. Among them, formic acid, the simplest carboxylic acid, has recently emerged as one of the most [...] Read more.
The production of H2 from the so-called Liquid Organic Hydrogen Carriers (LOHC) has recently received great focus as an auspicious option to conventional hydrogen storage technologies. Among them, formic acid, the simplest carboxylic acid, has recently emerged as one of the most promising candidates. Catalysts based on Pd nanoparticles are the most fruitfully investigated, and, more specifically, excellent results have been achieved with bimetallic PdAg-based catalytic systems. The enhancement displayed by PdAg catalysts as compared to the monometallic counterpart is ascribed to several effects, such as the formation of electron-rich Pd species or the increased resistance against CO-poisoning. Aside from the features of the metal active phases, the properties of the selected support also play an important role in determining the final catalytic performance. Among them, the use of carbon materials has resulted in great interest by virtue of their outstanding properties and versatility. In the present review, some of the most representative investigations dealing with the design of high-performance PdAg bimetallic heterogeneous catalysts are summarised, paying attention to the impact of the features of the support in the final ability of the catalysts towards the production of H2 from formic acid. Full article
(This article belongs to the Special Issue Advanced Catalysis in Hydrogen Production from Formic Acid and Methanol)
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