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Nanomaterials
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Applications of Nanocatalysts in Biomass Conversion
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Applications of Nanocatalysts in Biomass Conversion

A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Energy and Catalysis".

Deadline for manuscript submissions: closed (30 September 2021) | Viewed by 24040

Special Issue Editors

Prof. Dr. Juan Carlos Serrano-Ruiz

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Guest Editor
Department of Engineering, University Loyola Andalucía, 41014 Seville, Spain
Interests: biomass conversion; CO2 valorization; catalysis; energy storage; hydrogen technologies
Special Issues, Collections and Topics in MDPI journals
Dr. Manuel Antonio Diaz-Perez

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Guest Editor
Department of Engineering, University Loyola Andalucía, Seville, Spain
Interests: catalysis; electrochemistry; reforming of bioalcohols; biomass conversion; valorization of CO2

Special Issue Information

Dear Colleagues,

Concerns about depleting fossil fuels and global warming effects are pushing our society to search for new renewable sources of energy with the potential to substitute coal, natural gas, and petroleum. In this sense, biomass—the only renewable source of carbon available on Earth—is the perfect replacement for petroleum in the production of fuels and chemicals. In the last decades, heterogeneous catalysis has played a central role in the rapid development of the petrochemical industry. Similarly, heterogeneous catalysis has been key in moving forward technologies for the conversion of biomass (and derivatives) into fuels and chemicals. However, the different chemical compositions of biomass, compared to petroleum, pose new requirements regarding catalysts. Thus, when applied to biomass conversion processes, water tolerance, multifunctionality, robustness, and resistance to impurities become important features. Controlling the shape and morphology of these solids at the nanoscale is also a relevant factor for controlling selectivity and directing synthesis towards obtaining the desired products.

This Special Issue welcomes manuscripts dealing with the utilization of nanocatalysts for the conversion of biomass or biomass-derived molecules (i.e., platform molecules) into fuels (e.g., bioethanol, biodiesel, liquid hydrocarbon fuels) and valuable chemicals. Papers providing physicochemical characterization of the nanocatalysts and insights into the structure–activity relationship are very much appreciated.

Prof. Dr. Juan Carlos Serrano-Ruiz
Dr. Manuel Antonio Diaz-Perez
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

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Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2400 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • biomass conversion
  • biofuels
  • biochemicals
  • heterogeneous catalysts
  • bioprocessing
  • platform molecules
  • catalytic upgrading

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Published Papers (6 papers)

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Research

17 pages, 4116 KiB  
Article
Study of the Metal–Support Interaction and Electronic Effect Induced by Calcination Temperature Regulation and Their Effect on the Catalytic Performance of Glycerol Steam Reforming for Hydrogen Production
by Songshan Zhu, Yunzhu Wang, Jichang Lu, Huihui Lu, Sufang He, Di Song, Yongming Luo and Jiangping Liu
Nanomaterials 2021, 11(11), 3149; https://doi.org/10.3390/nano11113149 - 22 Nov 2021
Cited by 14 | Viewed by 2821
Abstract
Steam reforming of glycerol to produce hydrogen is considered to be the very promising strategy to generate clean and renewable energy. The incipient-wetness impregnation method was used to load Ni on the reducible carrier TiO2 (P25). In the process of catalyst preparation, [...] Read more.
Steam reforming of glycerol to produce hydrogen is considered to be the very promising strategy to generate clean and renewable energy. The incipient-wetness impregnation method was used to load Ni on the reducible carrier TiO2 (P25). In the process of catalyst preparation, the interaction and electronic effect between metal Ni and support TiO2 were adjusted by changing the calcination temperature, and then the activity and hydrogen production of glycerol steam reforming reaction (GSR) was explored. A series of modern characterizations including XRD, UV-vis DRS, BET, XPS, NH3-TPD, H2-TPR, TG, and Raman have been applied to systematically characterize the catalysts. The characterization results showed that the calcination temperature can contribute to varying degrees of influences on the acidity and basicity of the Ni/TiO2 catalyst, the specific surface area, together with the interaction force between Ni and the support. When the Ni/TiO2 catalyst was calcined at 600 °C, the Ni species can be produced in the form of granular NiTiO3 spinel. Consequently, due to the moderate metal–support interaction and electronic activity formed between the Ni species and the reducible support TiO2 in the NiO/Ti-600C catalyst, the granular NiTiO3 spinel can be reduced to a smaller Ni0 at a lower temperature, and thus to exhibit the best catalytic performance. Full article
(This article belongs to the Special Issue Applications of Nanocatalysts in Biomass Conversion)
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25 pages, 4286 KiB  
Article
Renewable Hydrocarbon Production from Waste Cottonseed Oil Pyrolysis and Catalytic Upgrading of Vapors with Mo-Co and Mo-Ni Catalysts Supported on γ-Al2O3
by Josué Alves Melo, Mirele Santana de Sá, Ainara Moral, Fernando Bimbela, Luis M. Gandía and Alberto Wisniewski, Jr.
Nanomaterials 2021, 11(7), 1659; https://doi.org/10.3390/nano11071659 - 24 Jun 2021
Cited by 18 | Viewed by 3821
Abstract
In this work, the production of renewable hydrocarbons was explored by the means of waste cottonseed oil (WCSO) micropyrolysis at 500 °C. Catalytic upgrading of the pyrolysis vapors was studied using α-Al2O3, γ-Al2O3, Mo-Co/γ-Al2O [...] Read more.
In this work, the production of renewable hydrocarbons was explored by the means of waste cottonseed oil (WCSO) micropyrolysis at 500 °C. Catalytic upgrading of the pyrolysis vapors was studied using α-Al2O3, γ-Al2O3, Mo-Co/γ-Al2O3, and Mo-Ni/γ-Al2O3 catalysts. The oxygen removal efficiency was much lower in non-catalytic pyrolysis (18.0%), whilst γ-Al2O3 yielded a very high oxygen removal efficiency (91.8%), similar to that obtained with Mo-Co/γ-Al2O3 (92.8%) and higher than that attained with Mo-Ni/γ-Al2O3 (82.0%). Higher conversion yields into total renewable hydrocarbons were obtained with Mo-Co/γ-Al2O3 (61.9 wt.%) in comparison to Mo-Ni/γ-Al2O3 (46.6%). GC/MS analyses showed a relative chemical composition of 31.3, 86.4, and 92.6% of total renewable hydrocarbons and 58.7, 7.2, and 4.2% of oxygenated compounds for non-catalytic bio-oil (BOWCSO), BOMoNi and BOMoCo, respectively. The renewable hydrocarbons that were derived from BOMoNi and BOMoCo were mainly composed by olefins (35.3 and 33.4%), aromatics (31.4 and 28.9%), and paraffins (13.8 and 25.7%). The results revealed the catalysts’ effectiveness in FFA decarbonylation and decarboxylation, as evidenced by significant changes in the van Krevelen space, with the lowest O/C ratio values for BOMoCo and BOMoNi (O/C = 0–0.10) in relation to the BOWCSO (O/C = 0.10–0.20), and by a decrease in the presence of oxygenated compounds in the catalytic bio-oils. Full article
(This article belongs to the Special Issue Applications of Nanocatalysts in Biomass Conversion)
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16 pages, 5217 KiB  
Article
Free-Standing rGO-CNT Nanocomposites with Excellent Rate Capability and Cycling Stability for Na2SO4 Aqueous Electrolyte Supercapacitors
by Xiaohan Du, Zhen Qin and Zijiong Li
Nanomaterials 2021, 11(6), 1420; https://doi.org/10.3390/nano11061420 - 28 May 2021
Cited by 28 | Viewed by 4211
Abstract
Facing the increasing demand for various renewable energy storage devices and wearable and portable energy storage systems, the research on electrode materials with low costs and high energy densities has attracted great attention. Herein, free-standing rGO-CNT nanocomposites have been successfully synthesized by a [...] Read more.
Facing the increasing demand for various renewable energy storage devices and wearable and portable energy storage systems, the research on electrode materials with low costs and high energy densities has attracted great attention. Herein, free-standing rGO-CNT nanocomposites have been successfully synthesized by a facile hydrothermal method, in which the hierarchical porous network nanostructure is synergistically assembled by rGO nanosheets and CNT with interlaced network distribution. The rGO-CNT composite electrodes with synergistic enhancement of rGO and CNT exhibit high specific capacitance, excellent rate capability, exceptional conductivity and outstanding long-term cycling stability, especially for the optimal rGO-CNT30 electrode. Applied to a symmetric supercapacitor systems (SSS) assembled with an rGO-CNT30 electrode and with 1 M Na2SO4 aqueous solution as the electrolyte, the SSS possesses a high energy density of 12.29 W h kg−1 and an outstanding cycling stability, with 91.42% of initial specific capacitance after 18,000 cycles. Results from these electrochemical properties suggest that the rGO-CNT30 nanocomposite electrode is a promising candidate for the development of flexible and lightweight high-performance supercapacitors. Full article
(This article belongs to the Special Issue Applications of Nanocatalysts in Biomass Conversion)
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17 pages, 2500 KiB  
Article
The Importance of Thermal Treatment on Wet-Kneaded Silica–Magnesia Catalyst and Lebedev Ethanol-to-Butadiene Process
by Sang-Ho Chung, Adrian Ramirez, Tuiana Shoinkhorova, Ildar Mukhambetov, Edy Abou-Hamad, Selevedin Telalovic, Jorge Gascon and Javier Ruiz-Martínez
Nanomaterials 2021, 11(3), 579; https://doi.org/10.3390/nano11030579 - 26 Feb 2021
Cited by 8 | Viewed by 4250
Abstract
The Lebedev process, in which ethanol is catalytically converted into 1,3-butadiene, is an alternative process for the production of this commodity chemical. Silica–magnesia (SiO2–MgO) is a benchmark catalyst for the Lebedev process. Among the different preparation methods, the SiO2–MgO [...] Read more.
The Lebedev process, in which ethanol is catalytically converted into 1,3-butadiene, is an alternative process for the production of this commodity chemical. Silica–magnesia (SiO2–MgO) is a benchmark catalyst for the Lebedev process. Among the different preparation methods, the SiO2–MgO catalysts prepared by wet-kneading typically perform best owing to the surface magnesium silicates formed during wet-kneading. Although the thermal treatment is of pivotal importance as a last step in the catalyst preparation, the effect of the calcination temperature of the wet-kneaded SiO2–MgO on the Lebedev process has not been clarified yet. Here, we prepared and characterized in detail a series of wet-kneaded SiO2–MgO catalysts using varying calcination temperatures. We find that the thermal treatment largely influences the type of magnesium silicates, which have different catalytic properties. Our results suggest that the structurally ill-defined amorphous magnesium silicates and lizardite are responsible for the production of ethylene. Further, we argue that forsterite, which has been conventionally considered detrimental for the formation of ethylene, favors the formation of butadiene, especially when combined with stevensite. Full article
(This article belongs to the Special Issue Applications of Nanocatalysts in Biomass Conversion)
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14 pages, 2418 KiB  
Article
Insight into the Ex Situ Catalytic Pyrolysis of Biomass over Char Supported Metals Catalyst: Syngas Production and Tar Decomposition
by Mian Hu, Baihui Cui, Bo Xiao, Shiyi Luo and Dabin Guo
Nanomaterials 2020, 10(7), 1397; https://doi.org/10.3390/nano10071397 - 18 Jul 2020
Cited by 33 | Viewed by 4267
Abstract
Ex situ catalytic pyrolysis of biomass using char-supported nanoparticles metals (Fe and Ni) catalyst for syngas production and tar decomposition was investigated. The characterizations of fresh Fe-Ni/char catalysts were determined by TGA, SEM–EDS, Brunauer–Emmett–Teller (BET), and XPS. The results indicated that nanoparticles metal [...] Read more.
Ex situ catalytic pyrolysis of biomass using char-supported nanoparticles metals (Fe and Ni) catalyst for syngas production and tar decomposition was investigated. The characterizations of fresh Fe-Ni/char catalysts were determined by TGA, SEM–EDS, Brunauer–Emmett–Teller (BET), and XPS. The results indicated that nanoparticles metal substances (Fe and Ni) successfully impregnated into the char support and increased the thermal stability of Fe-Ni/char. Fe-Ni/char catalyst exhibited relatively superior catalytic performance, where the syngas yield and the molar ratio of H2/CO were 0.91 Nm3/kg biomass and 1.64, respectively. Moreover, the lowest tar yield (43.21 g/kg biomass) and the highest tar catalytic conversion efficiency (84.97 wt.%) were also obtained under the condition of Ni/char. Ultimate analysis and GC–MS were employed to analyze the characterization of tar, and the results indicated that the percentage of aromatic hydrocarbons appreciably increased with the significantly decrease in oxygenated compounds and nitrogenous compounds, especially in Fe-Ni/char catalyst, when compared with no catalyst pyrolysis. After catalytic pyrolysis, XPS was employed to investigate the surface valence states of the characteristic elements in the catalysts. The results indicated that the metallic oxides (MexOy) were reduced to metallic Me0 as active sites for tar catalytic pyrolysis. The main reactions pathway involved during ex situ catalytic pyrolysis of biomass based on char-supported catalyst was proposed. These findings indicate that char has the potential to be used as an efficient and low-cost catalyst toward biomass pyrolysis for syngas production and tar decomposition. Full article
(This article belongs to the Special Issue Applications of Nanocatalysts in Biomass Conversion)
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21 pages, 3822 KiB  
Article
Niobium on BEA Dealuminated Zeolite for High Selectivity Dehydration Reactions of Ethanol and Xylose into Diethyl Ether and Furfural
by Deborah S. Valadares, Maria Clara H. Clemente, Elon F. de Freitas, Gesley Alex V. Martins, José A. Dias and Sílvia C. L. Dias
Nanomaterials 2020, 10(7), 1269; https://doi.org/10.3390/nano10071269 - 29 Jun 2020
Cited by 10 | Viewed by 3237
Abstract
In this work, we investigated the role of solid-state dealumination by (NH4)2SiF6 (25% Al removal and 13% Si insertion), the impregnation of niobium (10, 18, and 25 wt. %) on dealuminated *BEA (DB) zeolite and their catalytic properties [...] Read more.
In this work, we investigated the role of solid-state dealumination by (NH4)2SiF6 (25% Al removal and 13% Si insertion), the impregnation of niobium (10, 18, and 25 wt. %) on dealuminated *BEA (DB) zeolite and their catalytic properties in ethanol and xylose transformations. Among all the studied catalysts, 18%Nb-DB showed increased mesoporosity and external areas. A leveling effect in the number and strength of the proposed two sites (Brønsted and Lewis) present in the catalyst (n1 = 0.24 mmol g−1, −ΔH1 = 49 kJ mol−1, and n2 = 0.20 mmol g−1, –ΔH2 = 42 kJ mol−1) in the catalyst 18%Nb-DB, might be responsible for its good activity. This catalyst presented the highest selectivity for diethyl ether, DEE (97%) with 61% conversion after 50 ethanol pulses at 230 °C (turnover number, TON DEE = 1.15). These features allowed catalytically fruitful bonding of the ethanol molecules to the neighboring sites on the channels, facilitating bimolecular ether formation through a possible SN2 mechanism. The same catalyst was active and selective for transformation of xylose at 180 °C, showing 64% conversion and 51% selectivity for furfural (TON Furfural = 24.7) using water as a green solvent. Full article
(This article belongs to the Special Issue Applications of Nanocatalysts in Biomass Conversion)
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