Journal
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
Volume 7, Issue 17, Pages 14973-14981Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acssuschemeng.9b03190
Keywords
sulfonic acid-functionalized biochar; hydrophobicity; diazo method; alkylation; high-density biofuel
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Funding
- National Natural Science Foundation of China [21706112]
- Natural Science Foundation of Jiangxi Province [20171BAB213017]
- Postdoctoral Science Foundation of China [2017KY21, 2018T110660]
- Nanchang University
- Arizona State University
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Because H2O decreases the acidity of sulfonic acid-based catalysts and initiates catalytic side reactions, the catalytic activity and selectivity of these catalysts are often unsatisfactory in many reactions that generate H2O as a byproduct. Herein, for the first time, hydrophobic acid-functionalized biochar is prepared by a new route based on a two-step diazo grafting method using 4-aminobenzenesulfonic acid as the sulfonated agent and 4-tert-butylaniline as the hydrophobic agent. The acid density and hydrophobicity can be easily regulated by the amounts of benzenesulfonic acid and tert-butylbenzene groups, respectively. The resulting catalysts have a large specific surface area of 400-700 m(2)/g, high acid density of greater than 2.0 mmol/g, and strong hydrophobicity with an H2O contact angle of up to 136 degrees. Compared with Amberlyst-15 and H2SO4-sulfonated biochar, the hydrophobic acidic biochar exhibits higher activity and selectivity in the alkylation of 4-ethylphenol with phenylmethanol and of 2-methylfuran with cyclic ketones (cyclopentanone and cyclohexanone) for the production of high-density biofuels. The successful preparation of the hydrophobic acidic biochar not only results in an efficient catalyst for reaction systems in which H2O has a deleterious effect but also paves a way for the functional modification of carbonaceous materials.
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