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Hydrophobic Solid Acids and Their Catalytic Applications in Green and Sustainable Chemistry

Journal Article · · ACS Catalysis
 [1];  [2];  [3];  [4];  [5]
  1. Fuzhou Univ., Fuzhou (China). National Engineering Research Center of Chemical Fertilizer Catalyst (NERC−CFC), School of Chemical Engineering
  2. Nanchang Univ., Nanchang (China). Key Lab. of Poyang Lake Environment and Resource Utilization of Ministry of Education, School of Resources Environmental and Chemical Engineering
  3. Chinese Academy of Sciences (CAS), Wuhan (China). National Center for Magnetic Resonance in Wuhan, State Key Lab. of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Inst. of Physics and Mathematics
  4. Zhejiang Univ., Hangzhou (China). Dept. of Chemistry
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division

Acid catalysts are widely used in petrochemical reactions, the synthesis of fine chemicals, and biomass conversions in industry. To comply with the principles of green and sustainable chemistry, much attention is being paid to the replacement of traditional liquid acids with solid acid catalysts. Normally, solid acids exhibit hydrophilicity because of the unique hydrophilic nature of the acidic sites on their surfaces. Water, as a typical solvent, byproduct, or negative component in a variety of acid-catalyzed reactions, may be adsorbed on solid acids and then cause the deactivation of catalytic sites or hydrolysis of the frameworks. The development of solid acids with suitable hydrophobicity largely overcomes these issues and enhances their catalytic activities and reusability. This Review discusses some recent advances in the preparation of novel solid acids with controllable wettability and suitable hydrophobicity and highlights their application in catalyzing various reactions such as esterification, transesterification, acylation, condensation, hydration, and depolymerization of crystalline cellulose. In addition, this Review discusses how the hydrophobicity of solid acids is affected by their structures, surface characteristics, and acid centers, and determines the principles for designing solid acids with high catalytic activity and good reusability. It is instructive for researchers who are interested in designing new kinds of solid acids with improved efficiency and reusability for applications in green and sustainable chemistry.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1462863
Journal Information:
ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 1 Vol. 8; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (132)

Novel Solid Acid Catalysts: Sulfonic Acid Group-Functionalized Mesostructured Polymers journal August 2007
A Highly Ordered Mesoporous Aluminosilicate, CMI-10, with a Si/Al Ratio of One journal August 2006
Graphene and Graphene Oxide: Synthesis, Properties, and Applications journal June 2010
A Carbon Material as a Strong Protonic Acid journal May 2004
Ordered Mesoporous Polymers and Homologous Carbon Frameworks: Amphiphilic Surfactant Templating and Direct Transformation journal November 2005
Catalytic Properties of Hierarchical Mesoporous Zeolites Templated with a Mixture of Small Organic Ammonium Salts and Mesoscale Cationic Polymers journal May 2006
Water-Tolerant, Highly Active Solid Acid Catalysts Composed of the Keggin-Type Polyoxometalate H3PW12O40 Immobilized in Hydrophobic Nanospaces of Organomodified Mesoporous Silica journal October 2007
Depolymerization of Cellulose Using Solid Catalysts in Ionic Liquids journal October 2008
Mechanism of Glucose Isomerization Using a Solid Lewis Acid Catalyst in Water journal October 2010
NMR Signatures of the Active Sites in Sn-β Zeolite journal July 2014
Acid Hydrolysis of Cellulose as the Entry Point into Biorefinery Schemes journal December 2009
Transesterification to Biodiesel with Superhydrophobic Porous Solid Base Catalysts journal May 2011
Selective Catalytic Production of 5-Hydroxymethylfurfural from Glucose by Adjusting Catalyst Wettability journal January 2014
Proton Conductivity of SO3H-Functionalized Benzene-Periodic Mesoporous Organosilica journal March 2011
Physicochemical Characterisation and Catalytic Activity of Primary Amine Templated Aluminosilicate Mesoporous Catalysts journal November 1997
Mesoporous Sulfonic Acids as Selective Heterogeneous Catalysts for the Synthesis of Monoglycerides journal February 1999
Combined Alkyl and Sulfonic Acid Functionalization of MCM-41-Type Silica journal July 2000
Octadecyl immobilized H-ZSM-5-catalyzed ring-openings of epoxides with water in liquid phase accompanying shape-selective property journal January 1992
Hydrolysis of sugars catalyzed by water-tolerant sulfonated mesoporous silicas journal August 2005
Synthesis of a Novel Carbon Based Strong Acid Catalyst Through Hydrothermal Carbonization journal July 2009
Transesterification Catalyzed by Superhydrophobic–Oleophilic Mesoporous Polymeric Solid Acids: An Efficient Route for Production of Biodiesel journal June 2013
Catalytic application of hydrophobic properties of high-silica zeolites I. Hydrolysis of ethyl acetate in aqueous solution journal November 1981
Various reactions catalyzed by niobium compounds and materials journal December 1995
Synthesis of 7-hydroxycoumarins by Pechmann reaction using Nafion resin/silica nanocomposites as catalysts journal September 2003
Solid acid catalysis using ion-exchange resins journal November 2001
Water-tolerant catalysis of a silica composite of a sulfonic acid resin, Aciplex journal January 2000
Zeolite-promoted hydrolysis of cellulose in ionic liquid, insight into the mutual behavior of zeolite, cellulose and ionic liquid journal July 2012
Design and synthesis of hydrophobic and stable mesoporous polymeric solid acid with ultra strong acid strength and excellent catalytic activities for biomass transformation journal June 2013
Catalyzed production of biodiesel and bio-chemicals from brown grease using Ionic Liquid functionalized ordered mesoporous polymer journal September 2014
Sulfonated carbon nanotubes as a strong protonic acid catalyst journal September 2005
One-step synthesis of carbon functionalized with sulfonic acid groups using hydrothermal carbonization journal May 2010
Efficient mesoporous polymer based solid acid with superior catalytic activities towards transesterification to biodiesel journal September 2012
High-temperature synthesis of magnetically active and SO3H-functionalized ordered mesoporous carbon with good catalytic performance journal June 2012
Lewis acid properties of some metal salts for lactic acid formation in water: 31 P NMR spectroscopy with trimethylphosphine oxide as a molecular probe journal May 2014
Direct synthesis of mesoporous M-SBA-15 (M=Al, Fe, B, Cr) and application to 1-hexene oligomerization journal December 2009
Heteropolyanion-based ionic liquid-functionalized mesoporous copolymer catalyst for Friedel–Crafts benzylation of arenes with benzyl alcohol journal October 2014
Selective synthesis of Bisphenol-A over mesoporous MCM silica catalysts functionalized with sulfonic acid groups journal April 2004
Synthesis, characterization, and catalytic activity of sulfonic acid-functionalized periodic mesoporous organosilicas journal December 2004
Design of multifunctionalized mesoporous silicas for esterification of fatty acid journal January 2005
Transesterification of triacetin with methanol on Nafion® acid resins journal January 2007
Sulfonic acid-functionalized silica-coated magnetic nanoparticle catalysts journal October 2007
Surface modification of nano-sized HZSM-5 and HFER by pre-coking and silanization journal October 2007
Aqueous-sensitive reaction sites in sulfonic acid-functionalized mesoporous silicas journal March 2008
Efficient and stable solid acid catalysts synthesized from sulfonation of swelling mesoporous polydivinylbenzenes journal April 2010
PS-SO 3 H@phenylenesilica with yolk–double-shell nanostructures as efficient and stable solid acid catalysts journal December 2014
Superoleophilic nanoporous polymeric ionic liquids loaded with palladium acetate: Reactants enrichment and efficient heterogeneous catalysts for Suzuki–Miyaura coupling reaction journal December 2014
Synthesis and characterization of sulfonated single-walled carbon nanotubes and their performance as solid acid catalyst journal March 2008
Supported zirconium sulfate on carbon nanotubes as water-tolerant solid acid catalyst journal July 2007
Synthesis of SBA-15 type mesoporous organosilicas with diethylenebenzene in the framework and post-synthetic framework modification journal January 2007
Active solid acid catalysts prepared by sulfonation of carbonization-controlled mesoporous carbon materials journal September 2007
Acid strengths and catalytic activities of sulfonic acid on polymeric and silica supports journal April 2007
Superhydrophobic nanoporous polymers as efficient adsorbents for organic compounds journal April 2009
Direct Synthesis of Hierarchically Porous Metal–Organic Frameworks with High Stability and Strong Brønsted Acidity: The Decisive Role of Hafnium in Efficient and Selective Fructose Dehydration journal April 2016
Lewis Acid Catalysis Confined in Zeolite Cages as a Strategy for Sustainable Heterogeneous Hydration of Epoxides journal April 2016
Direct Syntheses of Ordered SBA-15 Mesoporous Silica Containing Sulfonic Acid Groups journal August 2000
Synthesis of Heteroatom Substituted SBA-15 by the “pH-Adjusting” Method journal February 2004
Sulfonated Ordered Mesoporous Carbon as a Stable and Highly Active Protonic Acid Catalyst journal May 2007
Magnetic Solid Sulfonic Acid Decorated with Hydrophobic Regulators: A Combinatorial and Magnetically Separable Catalyst for the Synthesis of α-Aminonitriles journal April 2014
Inorganic Solid Acids and Their Use in Acid-Catalyzed Hydrocarbon Reactions journal May 1995
Design and Preparation of Organic−Inorganic Hybrid Catalysts journal October 2002
Water-Tolerant Solid Acid Catalysts journal October 2002
Ordered Mesoporous and Microporous Molecular Sieves Functionalized with Transition Metal Complexes as Catalysts for Selective Organic Transformations journal August 2002
Lewis Acids:  From Conventional Homogeneous to Green Homogeneous and Heterogeneous Catalysis journal November 2003
Mesopore-Modified Zeolites:  Preparation, Characterization, and Applications journal March 2006
Chemical Routes for the Transformation of Biomass into Chemicals journal June 2007
Advances in the Synthesis and Catalytic Applications of Organosulfonic-Functionalized Mesostructured Materials journal September 2006
Polymer/Silica Nanocomposites: Preparation, Characterization, Properties, and Applications journal September 2008
Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering journal September 2006
Green Routes for Synthesis of Zeolites journal November 2013
Ion Exchange Resins: Catalyst Recovery and Recycle journal December 2008
Catalysis by Heteropoly Acids and Multicomponent Polyoxometalates in Liquid-Phase Reactions journal February 1998
From Microporous to Mesoporous Molecular Sieve Materials and Their Use in Catalysis journal October 1997
Niobium Compounds:  Preparation, Characterization, and Application in Heterogeneous Catalysis journal December 1999
“One-Pot” Synthesis of 5-(Hydroxymethyl)furfural from Carbohydrates using Tin-Beta Zeolite journal April 2011
Hybrid Sulfonic Acid Catalysts Based on Silica-Supported Poly(Styrene Sulfonic Acid) Brush Materials and Their Application in Ester Hydrolysis journal May 2011
Design and Synthesis of Mesoporous Polymer-Based Solid Acid Catalysts with Excellent Hydrophobicity and Extraordinary Catalytic Activity journal March 2012
Review on Recent Progress in Nitrogen-Doped Graphene: Synthesis, Characterization, and Its Potential Applications journal April 2012
Framework and Extraframework Tin Sites in Zeolite Beta React Glucose Differently journal November 2012
Cooperativity of Brønsted and Lewis Acid Sites on Zeolite for Glycerol Dehydration journal March 2014
Energetics: A New Field of Applications for Hydrophobic Zeolites journal August 2001
Al-Free Sn-Beta Zeolite as a Catalyst for the Selective Reduction of Carbonyl Compounds (Meerwein−Ponndorf−Verley Reaction) journal April 2002
Novel Brønsted Acidic Ionic Liquids and Their Use as Dual Solvent−Catalysts journal May 2002
Ordered Nanoporous Polymers from Polystyrene−Polylactide Block Copolymers journal October 2002
A Facile Aqueous Route to Synthesize Highly Ordered Mesoporous Polymers and Carbon Frameworks with Iad Bicontinuous Cubic Structure journal October 2005
Nb2O5·nH2O as a Heterogeneous Catalyst with Water-Tolerant Lewis Acid Sites journal March 2011
ZSM-5 Zeolite Single Crystals with b -Axis-Aligned Mesoporous Channels as an Efficient Catalyst for Conversion of Bulky Organic Molecules journal March 2012
Hydrophobic Zeolites for Biofuel Upgrading Reactions at the Liquid–Liquid Interface in Water/Oil Emulsions journal May 2012
Transesterification Catalyzed by Ionic Liquids on Superhydrophobic Mesoporous Polymers: Heterogeneous Catalysts That Are Faster than Homogeneous Catalysts journal September 2012
Efficient Utilization of Nanospace of Layered Transition Metal Oxide HNbMoO 6 as a Strong, Water-Tolerant Solid Acid Catalyst journal June 2008
Hydrolysis of Cellulose by Amorphous Carbon Bearing SO 3 H, COOH, and OH Groups journal August 2008
Crystal Facets Make a Profound Difference in Polyoxometalate-Containing Metal–Organic Frameworks as Catalysts for Biodiesel Production journal September 2015
Solvent-Free Preparation of Nanosized Sulfated Zirconia with Brønsted Acidic Sites from a Simple Calcination journal February 2005
Mesoporous Silica Materials with an Extremely High Content of Organic Sulfonic Groups and Their Comparable Activities with that of Concentrated Sulfuric Acid in Catalytic Esterification journal July 2006
Titania as an Early Transition Metal Oxide with a High Density of Lewis Acid Sites Workable in Water journal July 2013
Water Resistant, Catalytically Active Nb and Ta Isolated Lewis Acid Sites, Homogeneously Distributed by Direct Synthesis in a Beta Zeolite
  • Corma, Avelino; Llabrés i Xamena, Francesc X.; Prestipino, Carmelo
  • The Journal of Physical Chemistry C, Vol. 113, Issue 26, p. 11306-11315 https://doi.org/10.1021/jp902375n
journal July 2009
Hydration of cyclohexene by alkyl‐immobilized H‐ZSM‐5 catalyst in decalin–water system journal October 1998
Sn-zeolite beta as a heterogeneous chemoselective catalyst for Baeyer–Villiger oxidations journal July 2001
Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism journal October 1992
Green chemistry: Biodiesel made with sugar catalyst journal November 2005
Ordered porous materials for emerging applications journal June 2002
Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates journal June 2007
Polystyrene sulphonic acid resins with enhanced acid strength via macromolecular self-assembly within confined nanospace journal January 2014
Amphiphilic organosilane-directed synthesis of crystalline zeolite with tunable mesoporosity journal August 2006
Novel synthesis of porous carbons with tunable pore size by surfactant-templated sol–gel process and carbonisation journal January 2002
Versatile mesoporous carbonaceous materials for acid catalysis journal January 2007
The chemistry of graphene oxide journal January 2010
Sulfonated graphene as water-tolerant solid acid catalyst journal January 2011
Synthesis strategies in the search for hierarchical zeolites journal January 2013
Advancements in solid acid catalysts for biodiesel production journal January 2014
Conversion of fructose into 5-hydroxymethylfurfural catalyzed by recyclable sulfonic acid-functionalized metal–organic frameworks journal January 2014
Efficient biomass transformations catalyzed by graphene-like nanoporous carbons functionalized with strong acid ionic liquids and sulfonic groups journal January 2015
Nanoporous catalysts for biomass conversion journal January 2015
Potential and challenges of zeolite chemistry in the catalytic conversion of biomass journal January 2016
Sulfonic acid functionalised ordered mesoporous materials as catalysts for condensation and esterification reactions journal January 1998
Water-tolerant catalysis by Mo–Zr mixed oxides calcined at high temperatures journal January 1999
Direct syntheses of ordered SBA-15 mesoporous materials containing arenesulfonic acid groups journal April 2002
Sulfonic acid functionalized crystal-like mesoporous benzene–silica as a remarkable water-tolerant catalyst journal January 2009
Acid properties of solid acid catalysts characterized by solid-state 31P NMR of adsorbed phosphorous probe molecules journal January 2011
High-temperature synthesis of strong acidic ionic liquids functionalized, ordered and stable mesoporous polymers with excellent catalytic activities journal January 2012
Understanding the high catalytic activity of propylsulfonic acid-functionalized periodic mesoporous benzenesilicas by high-resolution 1H solid-state NMR spectroscopy journal January 2012
Sulfated graphene as an efficient solid catalyst for acid-catalyzed liquid reactions journal January 2012
Self-assembly synthesis of a high-content sulfonic acid group functionalized ordered mesoporous polymer-based solid as a stable and highly active acid catalyst journal January 2012
Depolymerization of crystalline cellulose catalyzed by acidic ionic liquids grafted onto sponge-like nanoporous polymers journal January 2013
Mesoporosity – a new dimension for zeolites journal January 2013
Environmentally friendly catalytic methods journal January 1996
Heteropoly Acids and Related Compounds as Catalysts for Fine Chemical Synthesis journal May 1995
Electric Field Effect in Atomically Thin Carbon Films journal October 2004
Production of Liquid Alkanes by Aqueous-Phase Processing of Biomass-Derived Carbohydrates journal June 2005
Conversion of Sugars to Lactic Acid Derivatives Using Heterogeneous Zeotype Catalysts journal April 2010
Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores journal January 1998
Ordered Mesoporous Polymers of Tunable Pore Size from Colloidal Silica Templates journal February 1999
Nafion-Silica Nanocomposites: A New Generation of Water-Tolerant Solid Acids of High Efficiency journal January 2008

Cited By (22)

SAPO-34/5A Zeolite Bead Catalysts for Furan Production from Xylose and Glucose journal November 2018
Natural Nanofibrous Cellulose-Derived Solid Acid Catalysts journal January 2019
Edge Chemistry of Armchair Graphene Nanoribbons Containing Sulfur Functional Groups: Towards an Understanding of the Spin‐Dependent Electrochemistry journal January 2020
Biochar as heterogeneous support for immobilization of Pd as efficient and reusable biocatalyst in C–C coupling reactions journal August 2019
Conversion of Sugars and Biomass to Furans Using Heterogeneous Catalysts in Biphasic Solvent Systems journal September 2018
Design of Ordered Mesoporous Sulfonic Acid Functionalized ZrO 2 /organosilica Bifunctional Catalysts for Direct Catalytic Conversion of Glucose to Ethyl Levulinate journal September 2018
The Effect of Surface Wettability and Coalescence Dynamics in Catalytic Performance and Catalyst Preparation: A Review journal February 2019
“Click” Silica‐Supported Sulfonic Acid Catalysts with Variable Acid Strength and Surface Polarity journal April 2019
An Effective Heterogeneous Catalyst of [BMIM] 3 PMo 12 O 40 for Selective Sugar Epimerization journal April 2018
Synergy of B and Al Dopants in Mesoporous MFI Nanocrystals for Highly Selective Alcoholysis of Furfuryl Alcohol into Ethyl Levulinate journal April 2019
Synergetic combination of H 2 Zr 1 PW 12 O 40 and Sn‐Beta as potential solid acid catalyst for direct one‐step transformation of glucose to ethyl levulinate, a biofuel additive journal January 2019
Porous and efficient polymeric solid acid synthesized from sulfonation of nanoporous polymer journal August 2019
A convenient approach directly from triglycerides toward the producing of thia-wax esters as bio- and chemical raw materials journal August 2019
Advances in porous and nanoscale catalysts for viable biomass conversion journal January 2019
Supported ionic liquid phase (SILP) facilitated gas-phase enzyme catalysis – CALB catalyzed transesterification of vinyl propionate journal January 2018
Catalytic use of layered materials for fine chemical syntheses journal January 2019
A porous Brønsted superacid as an efficient and durable solid catalyst journal January 2018
Design of nitrogen-doped graphitized 2D hierarchical porous carbons as efficient solid base catalysts for transesterification to biodiesel journal January 2020
Cycloaddition of CO 2 with epoxides and esterification reactions using the porous redox catalyst Co-POM@MIL-101(Cr) journal January 2019
Nanocomposite of hydrophobic cellulose aerogel/graphene quantum dot/Pd: synthesis, characterization, and catalytic application journal January 2019
Preparation of sulfonated ordered mesoporous carbon catalyst and its catalytic performance for esterification of free fatty acids in waste cooking oils journal January 2019
Covalent Organic Frameworks: Promising Materials as Heterogeneous Catalysts for C-C Bond Formations journal September 2018

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