Climate change and the depletion of fossil fuels increase the demand for sustainable energy. Biodiesel synthesized using heterogeneous acid catalysts is a promising clean-energy carrier that supports a circular carbon economy. Herein, the efficient synthesis of biodiesel is reported using a reusable solid acid graphene catalyst functionalized with a natural aminosulfonic acid. Experimental and theoretical studies reveal the key role of functionalities that simultaneously contain amino and sulfonate groups, which impart superior acidity. Excellent activity and selectivity for oleic acid conversion to oleic acid methyl esters (a sustainable biofuel) are obtained, offering a strategy for achieving improved catalytic performance compared to earlier or benchmark catalysts in the field. Notably, the catalyst also effectively converts common vegetable oils into biodiesel via transesterification and facilitates carbohydrate dehydration to value-added chemicals, demonstrating broad applicability. Two additional variants of aminosulfonic acid-functionalized graphene show similar activity, confirming the crucial role of these functionalities in achieving high acidity and catalytic performance. The development of such potent, recyclable catalysts is crucial because acid catalysis is highly versatile, underpinning many biological and synthetic transformations.

IT4InnovationsVŠB Technical University of Ostrava 17 listopadu 2172 15 Ostrava 708 00 Poruba Czech

Nanotechnology Centre Centre for Energy and Environmental Technologies VŠB Technical University of Ostrava 17 listopadu 2172 15 Poruba 708 00 Ostrava Czech

Regional Centre of Advanced Technologies and MaterialsCzech Advanced Technology and Research Institute Palacký University in Olomouc Šlechtitelů 27 78371 Olomouc Czech

See more in PubMed

Davis S. J., Lewis N. S., Shaner M., Aggarwal S., Arent D., Azevedo I. L., Benson S. M., Bradley T., Brouwer J., Chiang Y.‐M., Clack C. T. M., Cohen A., Doig S., Edmonds J., Fennell P., Field C. B., Hannegan B., Hodge B.‐M., Hoffert M. I., Ingersoll E., Jaramillo P., Lackner K. S., Mach K. J., Ogden M. J., Peterson P. F., Sanchez D. L., Sperling D., Stagner J., Trancik J. E., et al. Science 2018, 360, eaas9793. PubMed

Timothy Searchinger O. J., Dumas P., Kastner T., Wirsenius S., Nature 2022, 612, 27. PubMed

National Academies of Sciences, Engineering, and Medicine , in Proc. of a Workshop–in Brief, The National Academies Press, Washington, DC: 2023.

Kohse‐Höinghaus K., Osswald P., Cool T. A., Kasper T., Hansen N., Qi F., Westbrook C. K., Westmoreland P. R., Angew. Chem. Int. Edit. 2010, 49, 3572. PubMed

European Union , Off. J. Eur. Union 2018, L 328, 82.

Lee A. F., Bennett J. A., Manayil J. C., Wilson K., Chem. Soc. Rev. 2014, 43, 7887. PubMed

Singh D., Sharma D., Soni S. L., Sharma S., Sharma P. K., Jhalani A., Fuel 2020, 262, 116553.

Guo Y., Delbari S. A., Sabahi Namini A., Le Q. V., Park J. Y., Kim D., Varma R. S., Jang H. W., T‐Raissi A., Shokouhimehr M., Li C., Mol. Catal. 2023, 547, 113362.

Nakajima K., Hara M., ACS Catal. 2012, 2, 1296.

Yao P. C., Gong H., Wu Z. Y., Fu H. Y., Li B., Zhu B., Ji J. W., Wang X. Y., Xu N., Tang C. J., Zhang H. G., Zhu J., Nat. Sustainability 2022, 5, 348.

Trickett C. A., Osborn Popp T. M., Su J., Yan C., Weisberg J., Huq A., Urban P., Jiang J., Kalmutzki M. J., Liu Q., Baek J., Head‐Gordon M. P., Somorjai G. A., Reimer J. A., Yaghi O. M., Nat. Chem. 2019, 11, 170. PubMed

Corma A., Iborra S., Velty A., Chem. Rev. 2007, 107, 2411. PubMed

Toda M., Takagaki A., Okamura M., Kondo J. N., Hayashi S., Domen K., Hara M., Nature 2005, 438, 178. PubMed

Ogino I., Suzuki Y., Mukai S. R., ACS Catal. 2015, 5, 4951.

Zhang X., Zhao Y., Xu S., Yang Y., Liu J., Wei Y., Yang Q., Nat. Commun. 2014, 5, 3170. PubMed

Klare H. F. T., Oestreich M., J. Am. Chem. Soc. 2021, 143, 15490. PubMed

Xu H., Zuend S. J., Woll M. G., Tao Y., Jacobsen E. N., Science 2010, 327, 986. PubMed PMC

Cheruvathoor Poulose A., Medveď M., Bakuru V. R., Sharma A., Singh D., Kalidindi S. B., Bares H., Otyepka M., Jayaramulu K., Bakandritsos A., Zbořil R., Nat. Commun. 2023, 14, 1373. PubMed PMC

Bakandritsos A., Pykal M., Blonski P., Jakubec P., Chronopoulos D. D., Polakova K., Georgakilas V., Cepe K., Tomanec O., Ranc V., Bourlinos A. B., Zboril R., Otyepka M., ACS Nano 2017, 11, 2982. PubMed PMC

Gelbard G., Bres O., Vargas R. M., Vielfaure F., Schuchardt U. F., J. Am. Oil Chem. Soc. 1995, 72, 1239.

Killner M. H. M., Linck Y. G., Danieli E., Rohwedder J. J. R., Blumich B., Fuel 2015, 139, 240.

Wood G. P. F., Radom L., Petersson G. A., Barnes E. C., Frisch M. J., Montgomery J. A. Jr., J. Chem. Phys. 2006, 125, 094106. PubMed

Copeland C., Menon O., Majumdar D., Roszak S., Leszczynski J., Phys. Chem. Chem. Phys. 2017, 19, 24866. PubMed

Marenich A. V., Cramer C. J., Truhlar D. G., J. Phys. Chem. B 2009, 113, 6378. PubMed

Liptak M. D., Shields G. C., J. Am. Chem. Soc. 2001, 123, 7314. PubMed

Rouquerol J. R. F., Sing K.S.W., Llewellyn P., Maurin G., Adsorption by Powders and Porous Solids: Principles, Methodology and Applications, 2nd ed., Elsevier, Amsterdam: 2012.

Medveď M., Zoppellaro G., Ugolotti J., Matochová D., Lazar P., Pospíšil T., Bakandritsos A., Tuček J., Zbořil R., Otyepka M., Nanoscale 2018, 10, 4696. PubMed PMC

Mayo D. W., in Course Notes: Interpretation of Infrared and Raman Spectra (Eds: Mayo D. W., Miller F. A., Hannah R. W.), John Wiley & Sons, Inc., Hoboken, NJ: 2004, pp. 101–140.

Zaoralova D., Hruby V., Sedajova V., Mach R., Kupka V., Ugolotti J., Bakandritsos A., Medved M., Otyepka M., ACS Sustainability Chem. Eng. 2020, 8, 4764.

Suganuma S., Nakajima K., Kitano M., Yamaguchi D., Kato H., Hayashi S., Hara M., J. Am. Chem. Soc. 2008, 130, 12787. PubMed

Whitener K. E., Stine R., Robinson J. T., Sheehan P. E., J. Phys. Chem. C 2015, 119, 10507.

Dubecky M., Otyepková E., Lazar P., Karlicky F., Petr M., Cépe K., Banás P., Zboril R., Otyepka M., J. Phys. Chem. Lett. 2015, 6, 1430. PubMed

Ji J. Y., Zhang G. H., Chen H. Y., Wang S. L., Zhang G. L., Zhang F. B., Fan X. B., Chem. Sci. 2011, 2, 484.

Flores K. P., Omega J. L. O., Cabatingan L. K., Go A. W., Agapay R. C., Ju Y. H., Renewable Energy 2019, 130, 510.

Fukuhara K., Nakajima K., Kitano M., Hayashi S., Hara M., ChemCatChem 2015, 7, 3945.

Konwar L. J., Mäki‐Arvela P., Mikkola J. P., Chem. Rev. 2019, 119, 11576. PubMed

Nakajima K., Haraw M., Hayashi S., J. Am. Ceram. Soc. 2007, 90, 3725.

Noshadi I., Kanjilal B., Liu F. J., Appl. Catal. A‐Gen. 2016, 513, 19.

Liu Y. J., Lotero E., Goodwin J. G., J. Catal. 2006, 243, 221.

Konwar L. J., Boro J., Deka D., Renewable Sustainable Energy Rev. 2014, 29, 546.

Mo X., López D. E., Suwannakarn K., Liu Y., Lotero E., Goodwin J. G., Lu C. Q., J. Catal. 2008, 254, 332.

Hara M., Energy Environ. Sci. 2010, 3, 601.

Yu J. T., Dehkhoda A. M., Ellis N., Energy Fuel 2011, 25, 337.

Guan Q. Q., Li Y., Chen Y., Shi Y. Z., Gu J. J., Li B., Miao R. R., Chen Q. L., Ning P., RSC Adv. 2017, 7, 7250.

Stellwagen D. R., van der Klis F., van Es D. S., de Jong K. P., Bitter J. H., ChemSusChem 2013, 6, 1668. PubMed

Hara M., Yoshida T., Takagaki A., Takata T., Kondo J. N., Hayashi S., Domen K., Angew. Chem. Int. Edit. 2004, 43, 2955. PubMed

Hara M., Top. Catal. 2010, 53, 805.

Sheldon R. A., Green Chem. 2014, 16, 950.

Mika L. T., Cséfalvay E., Németh A., Chem. Rev. 2018, 118, 505. PubMed

van Putten R.‐J., van der Waal J. C., de Jong E., Rasrendra C. B., Heeres H. J., de Vries J. G., Chem. Rev. 2013, 113, 1499. PubMed

Mariscal R., Maireles‐Torres P., Ojeda M., Sádaba I., Granados M. L., Energy Environ. Sci. 2016, 9, 1144.

Kang S. M., Ye J., Zhang Y., Chang J., RSC Adv. 2013, 3, 7360.

Qi X., Guo H., Li L., Smith R. L. Jr., ChemSusChem 2012, 5, 2215. PubMed

Yu X., Peng L., Gao X., He L., Chen K., RSC Adv. 2018, 8, 15762. PubMed PMC

Upare P. P., Yoon J. W., Kim M. Y., Kang H. Y., Hwang D. W., Hwang Y. K., Kung H. H., Chang J. S., Green Chem. 2013, 15, 2935.

Hou Q. D., Li W. Z., Ju M. T., Liu L., Chen Y., Yang Q., RSC Adv. 2016, 6, 104016.

Liu R., Chen J., Huang X., Chen L., Ma L., Li X., Green Chem. 2013, 15, 2895.

Karimi B., Mirzaei H. M., Behzadnia H., Vali H., ACS Appl. Mater. Interfaces 2015, 7, 19050. PubMed

Duyckaerts N., Trotus I. T., Nese V., Swertz A. C., Auris S., Wiggers H., Schüth F., ChemCatChem 2015, 7, 2891.

Verma S., Baig R. B. N., Nadagouda M. N., Len C., Varma R. S., Green Chem. 2017, 19, 164. PubMed PMC

Wang Y., Delbecq F., Kwapinski W., Len C., Mol. Catal. 2017, 438, 167.

Millán G. G., Phiri J., Mäkelä M., Maloney T., Balu A. M., Pineda A., Llorca J., Sixta H., Appl. Catal. A‐Gen. 2019, 585, 117180.

Wang Y., Len T., Huang Y., Taboada A. D., Boa A. N., Ceballos C., Delbecq F., Mackenzie G., Len C., ACS Sustainable Chem. Eng. 2017, 5, 392.

Fúnez‐Núñez I., García‐Sancho C., Cecilia J. A., Moreno‐Tost R., Pérez‐Inestrosa E., Serrano‐Cantador L., Maireles‐Torres P., Appl. Catal. A‐Gen. 2019, 585, 117188.

Kumar S., Gawande M. B., Kopp J., Kment S., Varma R. S., Zbořil R., ChemSusChem 2020, 13, 5231. PubMed

Jia R., Ren J. W., Liu X. H., Lu G. Z., Wang Y. Q., J. Mater. Chem. A 2014, 2, 11195.

Wang Y., Wang D., Tan M. H., Jiang B., Zheng J. T., Tsubaki N., Wu M. B., ACS Appl. Mater. Interfaces 2015, 7, 26767. PubMed

Baig R. B. N., Verma S., Nadagouda M. N., Varma R. S., Sci. Rep. 2016, 6, 39387. PubMed PMC

Liu Y. W., Liu S. M., He D. F., Li N., Ji Y. J., Zheng Z. P., Luo F., Liu S. X., Shi Z., Hu C. W., J. Am. Chem. Soc. 2015, 137, 12697. PubMed

Hassan H. M. A., Betiha M. A., Mohamed S. K., El‐Sharkawy E. A., Ahmed E. A., Appl. Surf. Sci. 2017, 412, 394.

Zhang H. L., Luo X., Shi K. Q., Wu T., He F., Zhou S. B., Chen G. Z., Peng C., ChemSusChem 2017, 10, 3352. PubMed

Liu F. S., Ma X. L., Li H., Wang Y. Y., Cui P., Guo M., Yaxin H. L., Lu W. P., Zhou S. J., Yu M. Z., Fuel 2020, 266, 117149.

Peng L., Philippaerts A., Ke X. X., Van Noyen J., De Clippel F., Van Tendeloo G., Jacobs P. A., Sels B. F., Catal. Today 2010, 150, 140.

Geng L., Wang Y., Yu G., Zhu Y. X., Catal. Commun. 2011, 13, 26.