Article
Chemistry, Physical
Geraldo Ferreira David, Daniela Margarita Echeverri Delgadillo, Gabriel Abranches Dias Castro, Diana Catalina Cubides-Roman, Sergio Antonio Fernandes, Valdemar Lacerda Junior
Summary: An effective catalytic consortium consisting of a Lewis acid (NbCl5) and a Bronsted acid (p-sulfonic acid calix[4]arene (CX4SO(3)H)) was found to convert glucose to 5-hydroxymethylfurfural (HMF) with high yields (50%). The consortium catalyst, tested in a microwave-assisted reactor and biphasic system, achieved the best result using CX4SO(3)H/NbCl5 (5 wt%/7.5 wt%) with water/NaCl and MIBK (1:3) at 150 degrees C for 17.5 min. The recycling of the catalyst was successful for up to seven times without affecting the HMF yield.
Article
Engineering, Chemical
Haoxiang Zhu, Youdi Zhang, Xusheng Guo, Youwei Cheng, Lijun Wang, Xi Li
Summary: In this study, the factors influencing the one-pot production of HMF from glucose in an acetone-water solvent were experimentally investigated. By optimizing the parameters, a high HMF yield was achieved and an economic and efficient HMF production process was proposed, providing support for subsequent industrial demonstration development.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Elisa Garcia-Lopez, Francesca Rita Pomilla, Bartolomeo Megna, Maria Luisa Testa, Leonarda Francesca Liotta, Giuseppe Marci
Summary: The study found that in the presence of pristine Nb2O5 in water, fructose can be converted to HMF through catalytic dehydration with high yield and selectivity. Optimizing reaction conditions can improve both yield and selectivity, with the best results obtained using 1 g·L-1 of pristine Nb2O5.
Article
Chemistry, Physical
Maurino Magno de Jesus Junior, Sergio Antonio Fernandes, Emilio Borges, Bruno Eduardo Lobo Baeta, Fabio de Avila Rodrigues
Summary: The study proposed a robust reaction network to determine the kinetic parameters of glucose conversion to HMF, via fructose as intermediary, using niobium phosphate in an aqueous medium. The selectivity for HMF reached a maximum of 80.4% at 125 degrees C for 15 minutes according to experimental results, with satisfactory agreement between predicted compound concentrations from the model and experimental data.
MOLECULAR CATALYSIS
(2022)
Article
Chemistry, Physical
Rujeeluk Khumho, Satit Yousatit, Chawalit Ngamcharussrivichai
Summary: In this study, a novel solid base catalyst Nb2O5 supported on MCS was developed for the synthesis of HMF through one-pot glucose conversion in a biphasic solvent. The catalyst exhibited high dispersion, tiny crystallites of Nb2O5, good textural properties, and the presence of Bronsted and Lewis acid sites with weak-to-medium strength, leading to superior glucose conversion and HMF yield compared to traditional catalysts. Its high catalytic stability and performance were attributed to the suitable ratio of Bronsted/Lewis acid sites and the hydrophobic properties generated from carbon moieties dispersed in the MCS nanocomposite.
Article
Engineering, Chemical
Haoxiang Zhu, Xusheng Guo, Yuxi Si, Qinrui Du, Youwei Cheng, Lijun Wang, Xi Li
Summary: In this study, the effects of acetone-water solvent on HMF production were investigated using experimental and theoretical methods. It was found that water increases substrate concentration and accelerates reaction rate through intermolecular hydrogen transfer, while acetone increases the population of high-reactive fructofuranose isomers, thus improving HMF yield. Therefore, water and acetone play a synergistic role in HMF preparation.
CHEMICAL ENGINEERING SCIENCE
(2023)
Article
Chemistry, Physical
Niuniu Zhu, Manyu Zhang, Guo Qiu, Hongyu Tian, Yongguo Liu
Summary: The synthesis of highly active niobium-modified montmorillonite catalysts and their application in the conversion of cellobiose and sucrose to 5-hydroxymethylfurfural (5-HMF) is reported. The presence of Lewis and Bronsted acid sites on the Nb-Mont catalyst facilitates the hydrolysis of substrates and plays a crucial role in the isomerization and dehydration processes. The catalytic approach provides a promising strategy for the efficient synthesis of 5-HMF from carbohydrates.
MOLECULAR CATALYSIS
(2022)
Article
Agricultural Engineering
Qing Qing, Wenxuan Wu, Xiaoran Tao, Zhuang Ma, Weigang He, Yuheng Tao, Liqun Wang
Summary: Aqueous choline chloride/acetone was developed as a green ternary solvent for catalytic conversion of glucose and raw corn stover into 5-HMF. The acidic choline chloride solution promoted the isomerization and dehydration of glucose to 5-HMF, while acetone acted as an efficient extracting solvent to remove 5-HMF from the aqueous phase. The composition of the ternary solvent system significantly affected the 5-HMF yield, reaction selectivity, and prevention of further degradation.
INDUSTRIAL CROPS AND PRODUCTS
(2022)
Article
Engineering, Chemical
Youdi Zhang, Haoxiang Zhu, Zefeng Ji, Youwei Cheng, Liping Zheng, Lijun Wang, Xi Li
Summary: This work presents experimental and kinetic modeling studies on fructose dehydration to 5-hydroxymethylfurfural (HMF) in the solution of mixed acetone and water, catalyzed by hydrochloric acid (HCl). A reaction scheme that added an intermediate was proposed. The established kinetic model considered various parameters and achieved a high yield under the optimized condition.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2022)
Article
Energy & Fuels
Qiaozhi Ma, Mingzhao Guan, Di Fan, Enchen Jiang
Summary: 5-hydroxymethylfurfural (5-HMF) is an important biomass-derived fuel precursor that can be efficiently converted from fructose in a biphasic system of LiBr hydrate/acetone. By adjusting Lewis acidity with AlCl3, a high yield of 5-HMF and glucose was directly produced from cellulose, achieving a promising carbon balance of 88.8%. Adsorption of 5-HMF from solvent via hyper-cross-linked polymer allows for efficient recycling of the product and the reaction system can be reused multiple times without losing selectivity.
Article
Chemistry, Applied
Katarzyna Morawa Eblagon, Anna Malaika, Karolina Ptaszynska, M. Fernando R. Pereira, Mieczyslaw Kozlowski, Jose Luis Figueiredo
Summary: The study focused on the cascade conversion of glucose to 5-hydroxymethylfurfural (HMF), a key platform commodity, as a sustainable approach for producing platform molecules from biomass. Bifunctional catalysts were prepared by depositing/precipitating Nb2O5 onto phosphorylated carbon xerogels, and the Lewis acid (LA) sites were adjusted by varying the Nb loading. The catalytic tests revealed that LA sites were important for selective glucose conversion, while the absence of LA sites led to glucose degradation to humin. The removal of strong Bronsted acid (BA) sites originating from Nb2O5 significantly increased the selectivity to HMF and achieved a maximum HMF yield of 31%.
Article
Chemistry, Multidisciplinary
Xuli Xu, Xiaojie Song, Xiaohui Liu, Haifeng Wang, Yongfeng Hu, Jie Xia, Jiacheng Chen, Mohsen Shakouri, Yong Guo, Yanqin Wang
Summary: The electrocatalytic oxidation of 5-hydroxymethyl-furfural (HMF) to produce 2,5-furandicarboxylic acid (FDCA) is an attractive route for bio-based polyesters. In this study, a highly efficient and stable nickel phosphate (Ni-3 (PO4)(2)) electrocatalyst was synthesized and compared with nickel hydroxide (Ni (OH)(2)). The introduction of phosphorus enhanced the charge transfer ability of the catalyst, and Ni-3(PO4)(2) showed higher activity in the oxidation of HMF than Ni (OH) 2.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Ricarda Kloth, Dmitry V. Vasilyev, Karl J. J. Mayrhofer, Ioannis Katsounaros
Summary: The study investigated the electrochemical conversion of HMF to BHH on different carbon electrodes, showing differences in product selectivity. It was found that the initial HMF concentration has an impact on reaction efficiency and product selectivity.
Article
Chemistry, Physical
Walid Hamza Saadaoui, Cecile Machut, Sebastien Rio, Sandra Bigot, Vincent Wiatz, Eric Monflier, Anne Ponchel
Summary: The direct conversion of glucose to 5-hydroxymethylfurfural was investigated using phosphated niobium oxide-carbon catalysts in a biphasic system. A facile approach for generating Nb-based composites with high metal loadings (around 20%) was developed through hydrothermal carbonization, calcination, and H3PO4 adsorption. Catalysts were characterized through various techniques, and NbP@C-RB30 and NbP@C-RB15 prepared using oligosaccharides and low water volumes exhibited higher efficiency for HMF production.
MOLECULAR CATALYSIS
(2023)
Article
Chemistry, Physical
Riddhi Mitra, Bhabani Malakar, Asim Bhaumik
Summary: This study presents a method for synthesizing 5-HMF from biomass resources, using catalysts without templates and organic molecules, achieving efficient conversion of fructose to 5-HMF.
Article
Engineering, Chemical
Marcio Jose da Silva, Diego Morais Chaves, Sukarno Olavo Ferreira, Rene Chagas da Silva, Jose Balena Gabriel Filho, Carlos Giovani Oliveira Bruziquesi, Abdulrahman A. Al-Rabiah
Summary: Phosphomolybdic acid salts were synthesized and evaluated as catalysts for the etherification reactions of glycerol with tert-butyl alcohol, with Sn(II) cations exchanged for their protons. Among the tested Sn(II) heteropoly salts, Sn3PMo12O40 showed the highest activity and selectivity towards glyceryl ethers, attributed to its greater Lewis acidity strength. Economic analysis indicated the viability of the process with a return on investment (ROI) of 30.7% for an annual production capacity of 30,000 metric tons.
CHEMICAL ENGINEERING SCIENCE
(2022)
Article
Materials Science, Multidisciplinary
Fabio C. Riemke, Catia L. Ucker, Neftali L. Carreno, Sergio da Silva Cava, Moises P. Teixeira, Humberto Fajardo, Jason G. Taylor, Marcio J. da Silva, Daniel C. Batalha, Cristiane W. Raubach
Summary: There is a growing interest in the search for environmentally friendly catalysts, particularly solid metal oxides. This study investigates the efficiency of SrTiO3 and the SrTiO3/Nb2O5 catalytic system in the oxidation process of thioanisole. The catalyst was synthesized through microwave-assisted hydrothermal process, and it was found that SrTiO3 nanoseeds have an inducing effect on the growth of Nb2O5. The SrTiO3/Nb2O5 catalyst exhibited high efficiency in the oxidation reaction of thioanisole.
MATERIALS CHEMISTRY AND PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Marcio Jose da Silva, Pedro Henrique de Andrade da Silva, Sukarno Olavo Ferreira, Rene Chagas da Silva, Carlos Giovani Oliveira Brusiquezi
Summary: Keggin heteropolyacids (HPAs) are versatile catalysts with adjustable properties through structural modification. This study evaluated the effects of structure modification on the catalytic performance by synthesizing a series of cobalt-polyoxometalates and found that K6CoW12O40 salt exhibited the highest activity and selectivity.
Article
Materials Science, Paper & Wood
Gabriel Abranches Dias Castro, Neide Paloma Goncalves Lopes, Sergio Antonio Fernandes, Marcio Jose da Silva
Summary: This paper presents a novel approach to synthesize 5-hydroxymethylfurfural (HMF) using metal-exchanged Keggin heteropolyacid salts as catalysts, resulting in improved yield and reduced environmental impact. The most efficient catalyst, Cu3/2PW12O40, showed high Lewis acidic strength allowing for coordination with water molecules and generation of H3O+ ions in the reaction medium.
Article
Chemistry, Physical
Marcio Jose da Silva, Claudio Junior Andrade Ribeiro, Castelo Bandane Vilanculo
Summary: This study assessed the activity of various Bronsted acid catalysts in the oxidative esterification reaction of benzaldehyde. It was found that the Vanadium-doped phosphomolybdic acid H5PMo10V2O40 showed the highest activity and selectivity. The doping of Vanadium increased the redox potential of the catalyst and accelerated the reaction step.
Article
Chemistry, Physical
Marcio Jose da Silva, Claudio Junior Andrade Ribeiro, Alana Alves Rodrigues
Summary: In this study, catalysts with the general formula H3+nPMo12-nVnO40 (n = 0, 1, 2 and 3) were used to replace molybdenum atoms with vanadium, and these catalysts were applied in the acetalization reaction of alkyl alcohols with terpene aldehyde. The focus was on evaluating the impact of vanadium load on the catalytic activity of phosphomolybdic acids and linking this effect with their structural properties. The results showed that the vanadium monosubstituted phosphomolybdic acid had the highest activity and selectivity in the formation of beta-citronellyl acetal. The effects of various reaction variables on conversion and selectivity were also investigated.
Article
Chemistry, Physical
Marcio Jose da Silva, Pedro Henrique da Silva Andrade
Summary: In this study, tungstic acid was used as a catalyst for the oxidation of terpene alcohols with hydrogen peroxide for the first time. The catalyst, which is simple, solid, and commercially available, efficiently converted borneol, geraniol, and nerol to camphor and epoxide products. Various reaction parameters were investigated, and conversions and selectivity greater than 90% were achieved using 1.0 mol% of H2WO4 after 2 hours of reaction at 90 degrees C. The catalyst could be easily recovered and reused without loss of activity. This is the first time that tungstic acid has been used as a catalyst for the oxidation reactions of terpene alcohols.
CATALYSIS SURVEYS FROM ASIA
(2023)
Review
Energy & Fuels
Marcio Jose da Silva, Neide Paloma Goncalves Lopes, Alana Alves Rodrigues
Summary: This article discusses the chemical transformation of glycerol to various compounds with high technological applications, especially in the fuel sector as bioadditives. The Keggin heteropolyacids (HPAs) are efficient catalysts in the syntheses of glycerol-derived bioadditives. However, their use as heterogeneous catalysts is hindered by their low surface area and solubility in polar solvents. Solid heteropoly salts, formed by converting HPAs to insoluble salts, have shown promise in reducing the cost and environmental impact of bioadditive synthesis processes.
Review
Chemistry, Inorganic & Nuclear
Marcio Jose da Silva, Alana Alves Rodrigues, Neide Paloma Goncalves Lopes
Summary: Keggin heteropolyacids can be converted to metal salts to improve their catalytic performance in oxidation reactions. The use of green oxidants reduces the environmental impact and has significant implications for various industries.
Article
Chemistry, Physical
Marcio Jose da Silva, Pedro Henrique da Silva Andrade, Tiago Almeida Silva, Mariana Beatriz Teixeira Diniz, Sukarno Olavo Ferreira, Rene Chagas da Silva, Eduardo Nery Duarte de Araujo
Summary: Silicotungstic acid-derived salts with Co(II) or Co(III) cations were used as catalysts in the oxidation reactions of terpenic alcohols. The (K5CoW12O40)-W-III salt exhibited the highest activity and selectivity towards the oxidation product camphor, achieving conversion and selectivity higher than 90%. The effects of temperature, stoichiometry of reactants, and catalyst load on the reaction were investigated, and a reaction pathway was proposed based on the experimental data.
Article
Environmental Sciences
Neide Paloma Goncalves Lopes, Fabiane Carvalho Ballotin, Ana Paula de Carvalho Teixeira, Rochel Montero Lago, Marcio Jose da Silva
Summary: In this study, an efficient renewable carbon catalyst obtained from bio-oil sulfonation was used for the first time to produce terpene acetals at room temperature. The catalyst was obtained by reacting bio-oil with sulfuric acid and showed very strong acid sites. The condensation reactions of ss-citronellal and alkyl alcohols achieved high conversion and selectivity, and the catalyst could be reused four times without significant activity loss. The use of renewable solid catalysts with recyclability and activity at room temperature is a positive aspect of this process.
WASTE AND BIOMASS VALORIZATION
(2023)
Article
Engineering, Chemical
Marcio Jose da Silva, Claudio Junior Andrade Ribeiro, Eduardo Nery de Araujo, Isadora Merighi Torteloti
Summary: In this study, vanadium-substituted cesium phosphomolybdate salts were synthesized and evaluated as catalysts for the acetalization of benzaldehyde with alkyl alcohols. The Cs4PMo11V1O40 salt exhibited the highest activity and selectivity, converting benzaldehyde into methyl benzyl acetal and benzoic acid without the need for an oxidant. The catalytic activity was found to be influenced by the Bronsted acidity of the catalyst. This solid catalyst offers advantages over liquid homogeneous catalysts, including low corrosiveness, minimal waste generation, and easy recovery/reuse, and provides a potential alternative route for acetal synthesis.
Article
Chemistry, Physical
Alana Alves Rodrigues, Marcio J. da Silva, Sukarno Olavo Ferreira, Rene Chagas da Silva, Tiago Almeida Silva, Eduardo Nery Duarte de Araujo
Summary: Phosphomolybdate salts were synthesized by exchanging the protons of the phosphomolybdic acid with various metal cations. These catalysts were evaluated for their oxidation reactions of terpene alcohols using hydrogen peroxide. The physicochemical properties of the catalysts were correlated with their performance, and AlPMo12O40 was found to be the most active and selective catalyst.
MOLECULAR CATALYSIS
(2023)
Article
Chemistry, Physical
Aldino Neto Venancio, Claudio Junior Andrade Ribeiro, Armanda Aparecida Julio, Luciano Menini, Luciana Alves Parreira, Gustavo Rodrigues de Souza, Marcio Jose da Silva
Summary: Inexpensive and simple commercial transition metal salts were evaluated as catalysts for the acetalization reaction between alkyl alcohols and beta-citronellal. FeCl3 was found to be the most active and selective catalyst, with reaction conversion and selectivity influenced by various reaction parameters and the oxidation state and type of anion in the salt. The high activity of FeCl3 was attributed to its strong Lewis acidity. This catalyst offers advantages over traditional liquid mineral acid catalysts and provides an alternative route for synthesizing alkyl terpene acetals.
REACTION KINETICS MECHANISMS AND CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Marcio Jose da Silva, Jonh Alexander Vergara Torres, Castelo Bandane Vilanculo
Summary: This study evaluated the application of vanadium-doped phosphomolybdic acids as catalysts in green oxidation reactions and assessed the effect of vanadium doping on the catalysts' performance.