Graphene-Based Nanomaterials as Heterogeneous Acid Catalysts: A Comprehensive Perspective
Abstract
:1. Introduction
Features | Sulfuric Acid | Amberlyst™-15 | G-NMs |
---|---|---|---|
Physical state | Liquid | Solid | Solid |
Acid activity | High | High | High |
Surface Area | - | Relatively low | High |
Operating conditions | Typically harsh | Relatively Mild | Variable a |
Diffusion/Leaching | None | Possible | Negligible |
Recoverability | Difficult | Easy b | Easy b |
Reusability/cycles | Difficult | Easy/Less cycles c | Easy/More cycles c |
Water tolerance/stability | High | Relatively low | High |
Cost-effectiveness | Cost-effective | Relatively expensive | Variable a |
Mass transfer | - | Relatively low | High |
Reaction selectivity | High | Variable a | Variable a |
Eco-friendly use | No | Yes | Yes |
Industrial use | Frequent | Selected d | Awaiting |
2. Graphite Oxide and Graphene Oxide (GO)
2.1. Synthesis and Structure
2.2. Acidic Properties of Graphite Oxide and GO
3. G-NMs vs. Sulfonation and Sulfation
3.1. Reduction of GO
3.1.1. Hydrazine (N2H4)
3.1.2. Sodium Borohydride (NaBH4)
3.1.3. Lithium Aluminum Hydride (LiAlH4)
3.2. Sulfonation of rGO and GO
Sulfonating Agents | Reducing Agents a | Reaction Conditions b | Acid Density c | Applications d | Ref. |
---|---|---|---|---|---|
4-Benzenediazonium sulfonate | N2H4·H2O | EtOH/H2O, H3PO2, 3–5 °C, 1.5 h | 1.55 mmol H+ g−1 | Hydrolysis of ethyl acetate | [82] |
Fuming sulfuric acid | NaBH4 | Autoclave, 180 °C, 24 h | 1.2 mmol H+ g−1 | (1) Esterification reactions (2) Peckmann reaction (3) Hydration reaction | [83] |
Chlorosulfonic acid | n-butyl lithium | ClSO3H, 0 °C, RT e, overnight, NaOH, HCl, H2O | - | Ester exchange reactions | [84] |
4-Benzenediazonium sulfonate | NaBH4 | 0 °C, 2 h, Hydrazine, 100 °C, 24 h | - | Synthesis of xanthenes and benzoxanthenes | [85] |
Chlorosulfonic acid | - | CHCl3, 70 °C, 4 h | 1.2 mmol H+ g−1 | Chemical conversion of biomass derived carbohydrates | [86] |
4-Benzenediazonium sulfonate | (i) NaBH4 (ii) N2H4 | RT e, overnight | 0.5–1.7 mmol H+ g−1 | Dehydration of xylose to furfural | [87] |
Ammonium sulfate | - | 235 °C, 30 min, argon atmosphere | EW f = 725 ± 5 g/mol | As support for metal nanocatalysts | [88] |
Sulfuric acid | Microwave irradiation, 190 °C | 160 °C, 5 h nitrogen atmosphere | 1.9 mmol H+ g−1 | Production of biofuels | [89] |
3.2.1. Diazonium Salt of Sulfanilic Acid; 4-Benzenediazonium Sulfonate
3.2.2. Fuming Sulfuric Acid
3.2.3. Chlorosulfonic Acid
3.2.4. Sulfuric Acid
4. Applications of G-NMs in Heterogeneous Acid Catalysis
4.1. Graphite Oxide as Acid Catalyst
4.1.1. Michael-Type Friedel-Crafts Addition
4.1.2. Polymerization
4.1.3. Synthesis of Dipyrromethanes
4.2. Graphene Oxide (GO) as Acid Catalyst
4.2.1. Hydration of Alkynes
4.2.2. Aza-Michael Addition
4.2.3. Ring Opening of Epoxides and Acetalization of Aldehydes
4.2.4. Conversion of Carbohydrates into 5-Ethoxymethylfurfural (EMF)
4.3. Sulfonated/Sulfated Graphene and Graphene Oxide (GO) as Acid Catalysts
4.3.1. Sulfonated Graphene and GO as Acid Catalysts Prepared by Diazonium Salt
Hydrolysis of Ethyl Acetate
Synthesis of Xanthenes and Benzoxanthenes
Dehydration of Xylose
4.3.2. Sulfonated Graphene as Acid Catalyst Prepared by Fuming Sulfuric Acid or Oleum
Esterification, Peckmann, and Hydration Reactions
4.3.3. Sulfated Graphene as Acid Catalyst Prepared by ClSO3H
Ester-Exchange Reactions
Chemical Conversion of Carbohydrates to Levulinic Acid (LA)
4.3.4. Sulfated rGO as Acid Catalyst Prepared by H2SO4
Conversion of HMF into Biofuels
5. Conclusions: Final Remarks
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Garg, B.; Bisht, T.; Ling, Y.-C. Graphene-Based Nanomaterials as Heterogeneous Acid Catalysts: A Comprehensive Perspective. Molecules 2014, 19, 14582-14614. https://doi.org/10.3390/molecules190914582
Garg B, Bisht T, Ling Y-C. Graphene-Based Nanomaterials as Heterogeneous Acid Catalysts: A Comprehensive Perspective. Molecules. 2014; 19(9):14582-14614. https://doi.org/10.3390/molecules190914582
Chicago/Turabian StyleGarg, Bhaskar, Tanuja Bisht, and Yong-Chien Ling. 2014. "Graphene-Based Nanomaterials as Heterogeneous Acid Catalysts: A Comprehensive Perspective" Molecules 19, no. 9: 14582-14614. https://doi.org/10.3390/molecules190914582