skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Critical design of heterogeneous catalysts for biomass valorization: current thrust and emerging prospects

Abstract

Catalysis in the heterogeneous phase plays a crucial role in the valorization of biorenewable substrates with controlled reactivity, efficient mechanical process separation, greater recyclability and minimization of environmental effects. In this minireview, we have critically analyzed the design aspects of catalysts with multifunctional properties in making biomass conversion processes more productive and sustainable. The catalytic systems have been categorized into subgroups such as metal oxides and phosphates, supported metals, functionalized porous materials, acidic and ion-exchange resins, zeolites and carbonaceous materials to discuss their structural features and active sites towards intrinsic reactivity and selectivity in the transformation of biomass intermediates via hydrolysis, dehydration, hydrodeoxygenation and oxidation pathways. Recent advances in photocatalytic materials for the oxidation of biomass-derived small molecules (such as sugars, alcohols, carboxylic acids) and lignin model compounds and the role of different heteroatoms in improving photo-electronic properties are discussed. The synergistic effect of metal nanoparticulate sites and acid–base supports of bimetallic catalytic systems in performing multistep cascade processes in one-pot are analyzed.

Authors:
 [1];  [2];  [2]
  1. National Univ. of Singapore (Singapore). Dept. of Chemical and Biomolecular Engineering
  2. Univ. of Delaware, Newark, DE (United States). Catalysis Center for Energy Innovation (CCEI), ISE Lab.
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1388762
Grant/Contract Number:  
SC0001004
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 6; Journal Issue: 20; Related Information: CCEI partners with the University of Delaware (lead); Brookhaven National Laboratory; California Institute of Technology; Columbia University; University of Delaware; Lehigh University; University of Massachusetts, Amherst; Massachusetts Institute of Technology; University of Minnesota; Pacific Northwest National Laboratory; University of Pennsylvania; Princeton University; Rutgers University; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 09 BIOMASS FUELS; catalysis (homogeneous); catalysis (heterogeneous); biofuels (including algae and biomass); bio-inspired; hydrogen and fuel cells; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats

De, Sudipta, Dutta, Saikat, and Saha, Basudeb. Critical design of heterogeneous catalysts for biomass valorization: current thrust and emerging prospects. United States: N. p., 2016. Web. doi:10.1039/c6cy01370h.
De, Sudipta, Dutta, Saikat, & Saha, Basudeb. Critical design of heterogeneous catalysts for biomass valorization: current thrust and emerging prospects. United States. https://doi.org/10.1039/c6cy01370h
De, Sudipta, Dutta, Saikat, and Saha, Basudeb. 2016. "Critical design of heterogeneous catalysts for biomass valorization: current thrust and emerging prospects". United States. https://doi.org/10.1039/c6cy01370h. https://www.osti.gov/servlets/purl/1388762.
@article{osti_1388762,
title = {Critical design of heterogeneous catalysts for biomass valorization: current thrust and emerging prospects},
author = {De, Sudipta and Dutta, Saikat and Saha, Basudeb},
abstractNote = {Catalysis in the heterogeneous phase plays a crucial role in the valorization of biorenewable substrates with controlled reactivity, efficient mechanical process separation, greater recyclability and minimization of environmental effects. In this minireview, we have critically analyzed the design aspects of catalysts with multifunctional properties in making biomass conversion processes more productive and sustainable. The catalytic systems have been categorized into subgroups such as metal oxides and phosphates, supported metals, functionalized porous materials, acidic and ion-exchange resins, zeolites and carbonaceous materials to discuss their structural features and active sites towards intrinsic reactivity and selectivity in the transformation of biomass intermediates via hydrolysis, dehydration, hydrodeoxygenation and oxidation pathways. Recent advances in photocatalytic materials for the oxidation of biomass-derived small molecules (such as sugars, alcohols, carboxylic acids) and lignin model compounds and the role of different heteroatoms in improving photo-electronic properties are discussed. The synergistic effect of metal nanoparticulate sites and acid–base supports of bimetallic catalytic systems in performing multistep cascade processes in one-pot are analyzed.},
doi = {10.1039/c6cy01370h},
url = {https://www.osti.gov/biblio/1388762}, journal = {Catalysis Science and Technology},
issn = {2044-4753},
number = 20,
volume = 6,
place = {United States},
year = {Fri Aug 26 00:00:00 EDT 2016},
month = {Fri Aug 26 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 95 works
Citation information provided by
Web of Science

Figures / Tables:

Scheme 1 Scheme 1: Key functionalities of heterogeneous catalysts required for fundamental reactions involved in biomass conversion.

Save / Share:

Works referenced in this record:

Catalytic Asymmetric Allylic Alkylation in Water with a Recyclable Amphiphilic Resin-Supported P,N -Chelating Palladium Complex
journal, March 2001


Hydrolysis of cellulose by cellulase-mimetic solid catalyst
journal, January 2012


Efficient Utilization of Nanospace of Layered Transition Metal Oxide HNbMoO 6 as a Strong, Water-Tolerant Solid Acid Catalyst
journal, June 2008


Dissolution of Cellose with Ionic Liquids
journal, May 2002

  • Swatloski, Richard P.; Spear, Scott K.; Holbrey, John D.
  • Journal of the American Chemical Society, Vol. 124, Issue 18, p. 4974-4975
  • https://doi.org/10.1021/ja025790m

Effect of phosphoric acid pretreatment on enzymatic hydrolysis of microcrystalline cellulose
journal, September 2010


Insights into the Interplay of Lewis and Brønsted Acid Catalysts in Glucose and Fructose Conversion to 5-(Hydroxymethyl)furfural and Levulinic Acid in Aqueous Media
journal, March 2013


Zeolite-Catalyzed Isomerization of Triose Sugars
journal, July 2009


Hydration of MCM-41 Studied by Sorption Calorimetry
journal, September 2007


Sulfonated porous organic polymer as a highly efficient catalyst for the synthesis of biodiesel at room temperature
journal, January 2016


Hydration of Halide Anions in Ion-Exchange Resin and Their Dissociation from Cationic Groups
journal, August 2004


Cellulose Hydrolysis by a New Porous Coordination Polymer Decorated with Sulfonic Acid Functional Groups
journal, June 2011


High-value chemicals obtained from selective photo-oxidation of glucose in the presence of nanostructured titanium photocatalysts
journal, December 2011


Room temperature versatile conversion of biomass-derived compounds by means of supported TiO2 photocatalysts
journal, January 2013


Biopolymer templated porous TiO2: An efficient catalyst for the conversion of unutilized sugars derived from hemicellulose
journal, September 2012


Cellulose Conversion under Heterogeneous Catalysis
journal, December 2008


Epitaxially Grown Layered MFI–Bulk MFI Hybrid Zeolitic Materials
journal, October 2012


Selective Bifunctional Catalytic Conversion of Cellulose over Reshaped Ni Particles at the Tip of Carbon Nanofibers
journal, May 2010


Catalytic oxidation of biomass derived 5-hydroxymethylfurfural (HMF) over Ru III -incorporated zirconium phosphate catalyst
journal, June 2016


Catalytic Behavior of Brønsted Acid Sites in MWW and MFI Zeolites with Dual Meso- and Microporosity
journal, December 2010


Gold Nanoparticles Located at the Interface of Anatase/Rutile TiO 2 Particles as Active Plasmonic Photocatalysts for Aerobic Oxidation
journal, April 2012


Xylose Isomerization to Xylulose and its Dehydration to Furfural in Aqueous Media
journal, October 2011


Photocatalytic selective oxidation of methanol to methyl formate in gas phase over titanium(IV) oxide in a flow-type reactor
journal, January 2010


Aerobic oxidation of 5-hydroxylmethylfurfural with homogeneous and nanoparticulate catalysts
journal, January 2012


Conversion of Xylose to Furfural Using Lewis and Brønsted Acid Catalysts in Aqueous Media
journal, August 2012


Aqueous-phase hydrodeoxygenation of sorbitol: A comparative study of Pt/Zr phosphate and PtReOx/C
journal, August 2013


Conversion of glucose into levulinic acid with solid metal(IV) phosphate catalysts
journal, August 2013


Hydrolysis of cellulose into glucose over carbons sulfonated at elevated temperatures
journal, January 2010


Towards the Sulfuric Acid of Solids
journal, October 1998


Depolymerization of Cellulose Assisted by a Nonthermal Atmospheric Plasma
journal, August 2011


Aerobic Oxidation of β-1 Lignin Model Compounds with Copper and Oxovanadium Catalysts
journal, November 2013


Catalytic conversion of cellulose to hexitols with mesoporous carbon supported Ni-based bimetallic catalysts
journal, January 2012


Catalytic Conversion of Cellulose into Sugar Alcohols
journal, August 2006


Efficient mechano-catalytic depolymerization of crystalline cellulose by formation of branched glucan chains
journal, January 2015


Catalytic C−O Bond Cleavage of 2-Aryloxy-1-arylethanols and Its Application to the Depolymerization of Lignin-Related Polymers
journal, September 2010


Dehydration of xylose into furfural over micro-mesoporous sulfonic acid catalysts
journal, January 2005


Toward a rational control of solid acid catalysis for green synthesis and biomass conversion
journal, January 2011


C-C or C-O Bond Cleavage in a Phenolic Lignin Model Compound: Selectivity Depends on Vanadium Catalyst
journal, January 2012


Platinum–cobalt bimetallic nanoparticles in hollow carbon nanospheres for hydrogenolysis of 5-hydroxymethylfurfural
journal, February 2014


A Heterogeneous Nickel Catalyst for the Hydrogenolysis of Aryl Ethers without Arene Hydrogenation
journal, December 2012

  • Sergeev, Alexey G.; Webb, Jonathan D.; Hartwig, John F.
  • Journal of the American Chemical Society, Vol. 134, Issue 50, p. 20226-20229
  • https://doi.org/10.1021/ja3085912

Tandem Lewis acid/Brønsted acid-catalyzed conversion of carbohydrates to 5-hydroxymethylfurfural using zeolite beta
journal, January 2016


A new approach for the production of 2,5-furandicarboxylic acid by in situ oxidation of 5-hydroxymethylfurfural starting from fructose
journal, August 2000


Total Hydrogenation of Furfural and 5-Hydroxymethylfurfural over Supported Pd–Ir Alloy Catalyst
journal, July 2014


Selective hydrolysis of cellulose into glucose over solid acid catalysts
journal, January 2008


Challenges of and Insights into Acid-Catalyzed Transformations of Sugars
journal, August 2014


Mechanisms for High Selectivity in the Hydrodeoxygenation of 5-Hydroxymethylfurfural over PtCo Nanocrystals
journal, May 2016


Photocatalysis with Organized Systems for the Oxofunctionalization of Hydrocarbons by O 2
journal, October 2002


Characterization and photocatalytic activity of K+-doped TiO2 photocatalysts
journal, March 2007


Metalloenzyme-like catalyzed isomerizations of sugars by Lewis acid zeolites
journal, June 2012


Effect of hydrogen donor on liquid phase catalytic transfer hydrogenation of furfural over a Ru/RuO2/C catalyst
journal, October 2014


Mesocellular Siliceous Foams with Uniformly Sized Cells and Windows
journal, January 1999


Titanium hydrogenphosphate: An efficient dual acidic catalyst for 5-hydroxymethylfurfural (HMF) production
journal, September 2014


Depolymerization of Cellulose Using Solid Catalysts in Ionic Liquids
journal, October 2008


Catalytic Transformations of Birch Kraft Pulp
journal, June 2012


Base metal-Pt alloys: A general route to high selectivity and stability in the production of biofuels from HMF
journal, December 2016


Glucose Activation by Transient Cr 2+ Dimers
journal, March 2010


Deglycerolization of Biodiesel Streams by Adsorption Over Silica Beds
journal, January 2007


Pretreatment and fractionation of corn stover by ammonia recycle percolation process
journal, December 2005


Tuneable porous carbonaceous materials from renewable resources
journal, January 2009


Highly Efficient and Selective Oxidation of Aromatic Alcohols Photocatalyzed by Nanoporous Hierarchical Pt/Bi 2 WO 6 in Organic Solvent-Free Environment
journal, January 2015


Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores
journal, January 1998


Bimetallic catalysts for upgrading of biomass to fuels and chemicals
journal, January 2012


Mechanism of Glucose Isomerization Using a Solid Lewis Acid Catalyst in Water
journal, October 2010


Non-Oxidative Vanadium-Catalyzed C-O Bond Cleavage: Application to Degradation of Lignin Model Compounds
journal, April 2010


Nanostructured Rutile TiO 2 for Selective Photocatalytic Oxidation of Aromatic Alcohols to Aldehydes in Water
journal, February 2008


Conversion of fructose, glucose and sucrose to 5-hydroxymethyl-2-furfural over mesoporous zirconium phosphate catalyst
journal, January 2015


Synthesis of macroreticular p-(ω-sulfonic-perfluoroalkylated)polystyrene ion-exchange resin and its application as solid acid catalyst
journal, March 2006


Efficient aqueous hydrogenation of biomass platform molecules using supported metal nanoparticles on Starbons®
journal, January 2009


The effect of TiO2-photocatalytic pretreatment on the biological production of ethanol from lignocelluloses
journal, May 2011


Chemocatalytic conversion of cellulose: opportunities, advances and pitfalls
journal, January 2011


A Unique Silk Mat-Like Structured Pd/CeO 2 as an Efficient Visible Light Photocatalyst for Green Organic Transformation in Water
journal, July 2013


Zinc-Assisted Hydrodeoxygenation of Biomass-Derived 5-Hydroxymethylfurfural to 2,5-Dimethylfuran
journal, September 2014


Efficient process for conversion of fructose to 5-hydroxymethylfurfural with ionic liquids
journal, January 2009


Selective photocatalytic degradation of aquatic pollutants by titania encapsulated into FAU-type zeolites
journal, April 2011


Framework and Extraframework Tin Sites in Zeolite Beta React Glucose Differently
journal, November 2012


A novel approach for lignin modification and degradation
journal, April 2010


Starch saccharification by carbon-based solid acid catalyst
journal, June 2010


Hydrolysis of Cellulose by Amorphous Carbon Bearing SO 3 H, COOH, and OH Groups
journal, August 2008


Self-Pillared, Single-Unit-Cell Sn-MFI Zeolite Nanosheets and Their Use for Glucose and Lactose Isomerization
journal, July 2015


Dehydration of fructose to 5-hydroxymethylfurfural in sub-critical water over heterogeneous zirconium phosphate catalysts
journal, October 2006


Biomass Recalcitrance: Engineering Plants and Enzymes for Biofuels Production
journal, February 2007


One-pot synthesis of 5-hydroxymethylfurfural: a significant biomass conversion over tin-promoted vanadium phosphate (Sn–VPO) catalyst
journal, January 2013


Selective, Nickel-Catalyzed Hydrogenolysis of Aryl Ethers
journal, April 2011


Selective conversion of furfural to methylfuran over silica-supported NiFe bimetallic catalysts
journal, November 2011


Which Controls the Depolymerization of Cellulose in Ionic Liquids: The Solid Acid Catalyst or Cellulose?
journal, February 2010


Cellulose pretreatment with 1-n-butyl-3-methylimidazolium chloride for solid acid-catalyzed hydrolysis
journal, November 2010


Biomass-Derived Porous Carbon Materials: Synthesis and Catalytic Applications
journal, May 2015


Selective Aerobic Oxidation of HMF to 2,5-Diformylfuran on Covalent Triazine Frameworks-Supported Ru Catalysts
journal, January 2015


Hydrolysis of Glucose to 5-Hydroxymethylfurfural
journal, September 2011


Heterogeneous photocatalytic reactions of organic acids and water. New reaction paths besides the photo-Kolbe reaction
journal, May 1984


Studies on the Vanadium-Catalyzed Nonoxidative Depolymerization of Miscanthus giganteus-Derived Lignin
journal, April 2013


Hydrogen spillover and the rate of heterogeneous catalytic hydrogenation. Quantitative model
journal, October 1986


A Mesoporous Carbon-Supported Pt Nanocatalyst for the Conversion of Lignocellulose to Sugar Alcohols
journal, November 2013


Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism
journal, October 1992


Synthesis of sugar alcohols by hydrolytic hydrogenation of cellulose over supported metal catalysts
journal, January 2011


Highly Active Mesoporous Nb-W Oxide Solid-Acid Catalyst
journal, February 2010


Effect of temperature and time in the hydrothermal treatment of HY zeolite
journal, March 2006


Tandem catalysis for the production of alkyl lactates from ketohexoses at moderate temperatures
journal, September 2015


Engineering Preformed Cobalt-Doped Platinum Nanocatalysts For Ultraselective Hydrogenation
journal, November 2008


Hydrothermal Synthesis of Zeolites with Three-Dimensionally Ordered Mesoporous-Imprinted Structure
journal, August 2011


Adsorption-Enhanced Hydrolysis of β-1,4-Glucan on Graphene-Based Amorphous Carbon Bearing SO 3 H, COOH, and OH Groups
journal, May 2009


Catalytical conversion of fructose and glucose into 5-hydroxymethylfurfural in hot compressed water by microwave heating
journal, July 2008


Chemical Routes for the Transformation of Biomass into Chemicals
journal, June 2007


Synthesis of 5-Hydroxymethylfurural from Carbohydrates using Large-Pore Mesoporous Tin Phosphate
journal, January 2014


Conversion of cellulose to glucose and levulinic acid via solid-supported acid catalysis
journal, April 2010


Cleavage and hydrodeoxygenation (HDO) of C–O bonds relevant to lignin conversion using Pd/Zn synergistic catalysis
journal, January 2013


Catalytic One-Pot Production of Small Organics from Polysaccharides
journal, April 2011


Microwave assisted rapid conversion of carbohydrates into 5-hydroxymethylfurfural catalyzed by mesoporous TiO2 nanoparticles
journal, December 2011


One-Pot Conversion of Cellulose into n -Hexane over the Ir-ReO x /SiO 2 Catalyst Combined with HZSM-5
journal, June 2014


Acid saccharification of ball-milled straw
journal, January 1989


Hydrolysis of biomass by magnetic solid acid
journal, January 2011


Sn-Beta zeolites with borate salts catalyse the epimerization of carbohydrates via an intramolecular carbon shift
journal, January 2012


Mechanistic Insights into Metal Lewis Acid-Mediated Catalytic Transfer Hydrogenation of Furfural to 2-Methylfuran
journal, June 2015


Synthesis of Self-Pillared Zeolite Nanosheets by Repetitive Branching
journal, June 2012


The critical role of heterogeneous catalysis in lignocellulosic biomass conversion
journal, January 2009


Selective Aerobic Oxidation Mediated by TiO 2 Photocatalysis
journal, October 2013


Conversion of Sugars to Lactic Acid Derivatives Using Heterogeneous Zeotype Catalysts
journal, April 2010


High Surface Area Nafion Resin/Silica Nanocomposites:  A New Class of Solid Acid Catalyst
journal, January 1996


Starbons: New Starch-Derived Mesoporous Carbonaceous Materials with Tunable Properties
journal, June 2006


Metal Chlorides in Ionic Liquid Solvents Convert Sugars to 5-Hydroxymethylfurfural
journal, June 2007


Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water
journal, March 2010


Mechanism of Photooxidation of Alcohol over Nb 2 O 5
journal, October 2009


Zeolite-Coated Mesostructured Cellular Silica Foams
journal, January 2003


Low-temperature ultrasound-promoted synthesis of Cr–TiO2-supported photocatalysts for valorization of glucose and phenol degradation from liquid phase
journal, May 2013


Shape-selective zeolite catalysis for bioplastics production
journal, July 2015


Copper-Zinc Alloy Nanopowder: A Robust Precious-Metal-Free Catalyst for the Conversion of 5-Hydroxymethylfurfural
journal, April 2015


Autocatalyzed and Ion-Exchange-Resin-Catalyzed Esterification Kinetics of Lactic Acid with Methanol
journal, February 2002


Selective photocatalytic oxidation of 4-substituted aromatic alcohols in water with rutile TiO2 prepared at room temperature
journal, January 2009


Role of Silanol Group in Sn-Beta Zeolite for Glucose Isomerization and Epimerization Reactions
journal, September 2013


Efficient Solid Acid Catalyst Containing Lewis and Brønsted Acid Sites for the Production of Furfurals
journal, May 2014


Fermentable sugars by chemical hydrolysis of biomass
journal, March 2010


Bifunctional Solid Catalysts for the Selective Conversion of Fructose to 5-Hydroxymethylfurfural
journal, May 2010


Pyrene-Based Porous Organic Polymers as Efficient Catalytic Support for the Synthesis of Biodiesels at Room Temperature
journal, July 2015


Effects of Catalyst Pore Structure and Acid Properties on the Dehydration of Glycerol
journal, November 2014


Photocatalytic Aerobic Oxidation of Alcohols on TiO2: The Acceleration Effect of a Brønsted Acid
journal, July 2010


Works referencing / citing this record:

Heterogeneous Bimetallic Catalysts for Upgrading Biomass-Derived Furans
journal, August 2018


Metal Catalysts for the Efficient Transformation of Biomass-derived HMF and Furfural to Value Added Chemicals
journal, March 2018


Conversion of Sugars and Biomass to Furans Using Heterogeneous Catalysts in Biphasic Solvent Systems
journal, September 2018


Environmentally Benign Approach for the Synthesis of Azo Dyes in the Presence of Mesoporous Sulfated Core‐Shell Zirconia‐Copper(I) Oxide Solid Acid Catalyst
journal, May 2019


Supported Gold Nanoparticles for Furfural Valorization in the Future Bio-based Industry
journal, June 2018


An Insight into the Valorization of Hemicellulose Fraction of Biomass into Furfural: Catalytic Conversion and Product Separation
journal, February 2020


Hf-based metal–organic frameworks as acid–base catalysts for the transformation of biomass-derived furanic compounds into chemicals
journal, January 2018


Heterogeneous Catalytic Upgrading of Biofuranic Aldehydes to Alcohols
journal, July 2019


Metal Carbides for Biomass Valorization
journal, February 2018


Bimetallic Nanoparticles in Alternative Solvents for Catalytic Purposes
journal, July 2017