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Advanced Biomass-Derived Catalysts

A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Carbon Materials".

Deadline for manuscript submissions: closed (20 October 2023) | Viewed by 9776

Special Issue Editors


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Guest Editor
Department of Chemical Engineering, School of Industrial Engineering, University of Málaga, 29016 Málaga, Spain
Interests: thermochemical processes; adsorption; heterogeneous catalysis; biorefinery; electrospinning/electrospray; residual biomass valorization; carbon materials; electrocatalysis
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Guest Editor
Department of Chemical Engineering, School of Industrial Engineering, University of Málaga, 29016 Málaga, Spain
Interests: biomass; carbon-based materials; activated carbons; carbon fibers; heterogeneous catalysis; biomass gasification; Fischer–Tropsch synthesis; carbon supports; photocatalysis

Special Issue Information

Dear Colleagues,

Due to diminishing petroleum reserves, unsteady market situation and the environmental concerns associated with utilization of fossil resources, the use of renewable sources for the production of energy, chemicals (biorefining) and materials has attracted considerable attention. In this sense, biomass residues, in addition to being interesting raw materials for the production of liquid fuels and chemicals, also present great potential as sustainable precursors of advanced catalytic materials, resulting in both a positive environmental and economic impact.

The possibilities of tailoring and controlling physical surface properties and porosity and of modifying surface chemistry via functionalization during the synthesis of biomass-derived catalysts, improving anchoring, immobilization, and dispersion of the active phases and enhancing chemical and thermal stability make these materials particularly relevant for many different applications. On the other hand, exploiting the diverse textures, architectures, and biomorphologies of different biomasses is also of great importance for catalytical applications, in order to fix diverse reactors geometries, avoid pressure drop or transport limitations and enhance mechanical resistance.

This Special Issue is aimed at covering the most recent research progress in the synthesis, functionalization, characterization, engineering, and application of advanced biomass-derived catalysts. Therefore, we encourage researchers to submit original research papers, reviews, short communications, and commentaries reflecting the state-of-the-art and future advances in this field, with particular emphasis on applications in heterogeneous catalysis, biocatalysis, photocatalysis, electrocatalysis, energy, environmental remediation, etc.

Prof. Dr. José Rodríguez Mirasol
Dr. María José Valero-Romero
Guest Editors

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Keywords

  • biomass-derived catalysts
  • catalyst synthesis
  • catalyst characterization
  • surface functionalization
  • biorefinery
  • heterogeneous catalysis
  • biocatalysts
  • photocatalysts
  • electrocatalysts
  • environmental remediation

Published Papers (6 papers)

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Research

14 pages, 9073 KiB  
Article
Proactive Effect of Algae-Based Graphene Support on the Oxygen Evolution Reaction Electrocatalytic Activity of NiFe
by María González-Ingelmo, Marcos Granda, Begoña Ruiz, Enrique Fuente, Uriel Sierra, Victoria G. Rocha, Zoraida González, Patricia Álvarez and Rosa Menéndez
Materials 2023, 16(24), 7641; https://0-doi-org.brum.beds.ac.uk/10.3390/ma16247641 - 14 Dec 2023
Cited by 1 | Viewed by 692
Abstract
The preparation of graphene materials from biomass resources is still a challenge, even more so if they are going to be employed as supports for electrocatalysts for water splitting. Herein, we describe the preparation and characterization of graphene oxides (GOs) from solid macroalgae [...] Read more.
The preparation of graphene materials from biomass resources is still a challenge, even more so if they are going to be employed as supports for electrocatalysts for water splitting. Herein, we describe the preparation and characterization of graphene oxides (GOs) from solid macroalgae waste obtained after processing an agar–agar residue. The structural and morphological characterization of the obtained GO confirm the presence of a lamellar material that is composed of few layers with an increased number of heteroatoms (including nitrogen) if compared with those observed in a GO obtained from graphite (reference). Three-dimensional electrodes were prepared from these GOs by depositing them onto a fibrous carbon paper, followed by electrodeposition of the catalyst, NiFe. The electrocatalytic performance of these hybrid systems for the oxygen evolution reaction (OER) showed a proactive effect of both graphene materials toward catalysis. Moreover, the electrode prepared from the algae-based graphene showed the highest electrocatalytic activity. This fact could be explained by the different structure of the algae-based graphene which, due to differences in the nucleation growth patterns and electroactive sites developed during the electrodeposition process, produced more reactive NiFe species (higher oxidation state). Full article
(This article belongs to the Special Issue Advanced Biomass-Derived Catalysts)
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19 pages, 7538 KiB  
Article
Preparatory Conditions Optimization and Characterization of Hierarchical Porous Carbon from Seaweed as Carbon-Precursor Using a Box—Behnken Design for Application of Supercapacitor
by Wein-Duo Yang, Jing-Xuan Wang, Yu-Tse Wu, Hsun-Shuo Chang and Horng-Huey Ko
Materials 2022, 15(16), 5748; https://0-doi-org.brum.beds.ac.uk/10.3390/ma15165748 - 20 Aug 2022
Viewed by 1159
Abstract
This study has developed an environmentally friendly, simple, and economical process by utilizing seaweed as a carbon precursor to prepare a hierarchical porous carbon for the application of a supercapacitor. In the carbonization process, the design of experiment (DOE) technology is used to [...] Read more.
This study has developed an environmentally friendly, simple, and economical process by utilizing seaweed as a carbon precursor to prepare a hierarchical porous carbon for the application of a supercapacitor. In the carbonization process, the design of experiment (DOE) technology is used to obtain the optimal preparatory conditions with the best electrochemical properties for the electrode materials of supercapacitors. Without using strong acid and alkali solution of the green process, NaCl is used as the pore structure proppant of seaweed (SW) for carbonization to obtain hierarchical porous carbon material to improve the pore size distribution and surface area of the material. In the experiment of SW activation, the interaction between factors has been explored by the response surface methodology (RSM) and Box–Behnken design, and the optimal conditions are found. The activated carbon with the specific surface area of 603.7 m2 g−1 and its capacitance reaching 110.8 F g−1 is successfully prepared. At a current density of 1 A g−1, the material still retains 95.4% of the initial capacitance after 10,000 cycles of stability testing. The hierarchical porous carbon material prepared by the design of experiment planning this green process has better energy storage properties than supercapacitors made of traditional carbon materials. Full article
(This article belongs to the Special Issue Advanced Biomass-Derived Catalysts)
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20 pages, 3348 KiB  
Article
A Kinetic Model Considering Catalyst Deactivation for Methanol-to-Dimethyl Ether on a Biomass-Derived Zr/P-Carbon Catalyst
by Javier Torres-Liñán, Ramiro Ruiz-Rosas, Juana María Rosas, José Rodríguez-Mirasol and Tomás Cordero
Materials 2022, 15(2), 596; https://0-doi-org.brum.beds.ac.uk/10.3390/ma15020596 - 13 Jan 2022
Cited by 3 | Viewed by 1803
Abstract
A Zr-loaded P-containing biomass-derived activated carbon (ACPZr) has been tested for methanol dehydration between 450 and 550 °C. At earlier stages, methanol conversion was complete, and the reaction product was mainly dimethyl ether (DME), although coke, methane, hydrogen and CO were also observed [...] Read more.
A Zr-loaded P-containing biomass-derived activated carbon (ACPZr) has been tested for methanol dehydration between 450 and 550 °C. At earlier stages, methanol conversion was complete, and the reaction product was mainly dimethyl ether (DME), although coke, methane, hydrogen and CO were also observed to a lesser extent. The catalyst was slowly deactivated with time-on-stream (TOS), but maintained a high selectivity to DME (>80%), with a higher yield to this product than 20% for more than 24 h at 500 °C. A kinetic model was developed for methanol dehydration reaction, which included the effect of the inhibition of water and the deactivation of the catalyst by coke. The study of stoichiometric rates pointed out that coke could be produced through a formaldehyde intermediate, which might, alternatively, decompose into CO and H2. On the other hand, the presence of 10% water in the feed did not affect the rate of coke formation, but produced a reduction of 50% in the DME yield, suggesting a reversible competitive adsorption of water. A Langmuir–Hinshelwood reaction mechanism was used to develop a kinetic model that considered the deactivation of the catalyst. Activation energy values of 65 and 51 kJ/mol were obtained for DME and methane production in the temperature range from 450 °C to 550 °C. On the other hand, coke formation as a function of time on stream (TOS) was also modelled and used as the input for the deactivation function of the model, which allowed for the successful prediction of the DME, CH4 and CO yields in the whole evaluated TOS interval. Full article
(This article belongs to the Special Issue Advanced Biomass-Derived Catalysts)
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11 pages, 1347 KiB  
Article
Sustainable Biocatalytic Procedure for Obtaining New Branched Acid Esters
by María Claudia Montiel, Miguel Asensi, Silvia Gimeno-Martos, Fuensanta Máximo and Josefa Bastida
Materials 2021, 14(22), 6847; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14226847 - 13 Nov 2021
Cited by 4 | Viewed by 1544
Abstract
Biocatalytic synthesis of 2-ethylhexyl 2-methylhexanoate is described in this work for the first time. This branched-chain ester is suitable for use at low temperatures in numerous applications. The immobilized lipase Novozym® 435 has demonstrated its ability to catalyze the ester synthesis from [...] Read more.
Biocatalytic synthesis of 2-ethylhexyl 2-methylhexanoate is described in this work for the first time. This branched-chain ester is suitable for use at low temperatures in numerous applications. The immobilized lipase Novozym® 435 has demonstrated its ability to catalyze the ester synthesis from 2-ethylhexanol and 2-methylhexanoic acid in a solvent-free medium. The high reaction times that are required result in a loss of alcohol by evaporation, which must be compensated for with an excess of this substrate if high conversions are to be achieved. Therefore, two strategies are established: 70 °C with a 10% excess of alcohol, which requires a longer operating time and provides conversions of 97%, and 80 °C with a 20% excess of alcohol, which allows for the achievement of a 99% conversion in a shorter time. The optimal reaction conditions have been chosen based on reusability of the enzyme, process productivity, green metrics and preliminary economic study. When the synthesis is carried out under the best conditions (70 °C, 10% molar excess of alcohol and six uses of the immobilized enzyme) a productivity of 203.84 kg product × kg biocatalyst−1 is attained. The biocatalytic procedure matches many of the objectives of “green chemistry” and is suitable to be scaled up and used in industrial manufacturing. Full article
(This article belongs to the Special Issue Advanced Biomass-Derived Catalysts)
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15 pages, 2648 KiB  
Article
H2 Production from Formic Acid Using Highly Stable Carbon-Supported Pd-Based Catalysts Derived from Soft-Biomass Residues: Effect of Heat Treatment and Functionalization of the Carbon Support
by Jessica Alejandra Chaparro-Garnica, Miriam Navlani-García, David Salinas-Torres, Emilia Morallón and Diego Cazorla-Amorós
Materials 2021, 14(21), 6506; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14216506 - 29 Oct 2021
Cited by 1 | Viewed by 1741
Abstract
The production of hydrogen from liquid organic hydrogen carrier molecules stands up as a promising option over the conventional hydrogen storage methods. In this study, we explore the potential of formic acid as a convenient hydrogen carrier. For that, soft-biomass-derived carbon-supported Pd catalysts [...] Read more.
The production of hydrogen from liquid organic hydrogen carrier molecules stands up as a promising option over the conventional hydrogen storage methods. In this study, we explore the potential of formic acid as a convenient hydrogen carrier. For that, soft-biomass-derived carbon-supported Pd catalysts were synthesized by a H3PO4-assisted hydrothermal carbonization method. To assess the impact of the properties of the support in the catalytic performance towards the dehydrogenation of formic acid, three different strategies were employed: (i) incorporation of nitrogen functional groups; (ii) modification of the surface chemistry by performing a thermal treatment at high temperatures (i.e., 900 °C); and (iii) combination on both thermal treatment and nitrogen functionalization. It was observed that the modification of the carbon support with these strategies resulted in catalysts with enhanced performance and outstanding stability even after six consecutive reaction cycles, thus highlighting the important effect of tailoring the properties of the support. Full article
(This article belongs to the Special Issue Advanced Biomass-Derived Catalysts)
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12 pages, 2949 KiB  
Article
Laminar N-Doped Carbon Materials from a Biopolymer for Use as a Catalytic Support for Hydrodechlorination Catalysts
by Cristina Ruiz-Garcia and Miguel A. Gilarranz
Materials 2021, 14(11), 3107; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14113107 - 05 Jun 2021
Cited by 1 | Viewed by 1768
Abstract
Nitrogen-doped porous carbons were prepared using a chitosan biopolymer as both a carbon and nitrogen precursor and metallic salts (CaCl2 and ZnCl2-KCl) as a templating agent with the aim of evaluating their performance as catalyst supports. Mixtures of chitosan and [...] Read more.
Nitrogen-doped porous carbons were prepared using a chitosan biopolymer as both a carbon and nitrogen precursor and metallic salts (CaCl2 and ZnCl2-KCl) as a templating agent with the aim of evaluating their performance as catalyst supports. Mixtures of chitosan and templating salts were prepared by simple grinding subjected to pyrolysis and finally washed with water to remove the salts. The resulting materials were characterized, showing that homogeneous nitrogen doping of carbon was achieved (7–9% wt.) thanks to the presence of a nitrogen species in the chitosan structure. A lamellar morphology was developed with carbon sheets randomly distributed and folded on themselves, creating slit-shaped pores. Substantial porosity was observed in both the micropore and mesopore range with a higher surface area and microporosity in the case of the materials prepared by ZnCl2-KCl templating and a larger size of mesopores in the case of ZnCl2. Catalysts with well-dispersed Pd nanoparticles (around 10 nm in diameter size) were synthesized using the chitosan-based carbons obtained both by salt templating and direct chitosan pyrolysis and tested in the aqueous phase hydrodechlorination of 4-chlorophenol. The fast and total removal of 4-chlorophenol was observed in the case of catalysts based on carbons obtained by templating with CaCl2 and ZnCl2-KCl in spite of the low metal content of the catalysts (0.25% Pd, wt.). Full article
(This article belongs to the Special Issue Advanced Biomass-Derived Catalysts)
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