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Greener and higher conversion of esterification via interfacial photothermal catalysis

Nature Sustainability volume 5, pages 348–356 (2022)Cite this article

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Abstract

Reversible chemical reactions such as industrial production of esters are governed by the equilibrium law. To improve the productivity of esterification, superfluous reactants and dehydrants are usually used to drive the reaction forward. However, these methods are not only energy intensive but also cause extra difficulty in the separation of final products. Here we propose a photothermal catalysis system based on a sulfonic acid-functionalized graphene oxide aerogel to increase the yield rate of esterification without excess reactants or dehydrants. As a result of local photothermal heating and different molecular bond affinities, the generated products are evaporated out of reactive sites, leading to a local excess of reactants and thereby thermodynamically driving the reaction in favour of ester generation. Specifically, an acetic acid conversion rate of 77% is achieved, which is significantly higher than the theoretical limit of 62.5%. Theoretical analysis reveals its substantial advantage in saving the energy for separating products when applied to the real industrial esterification reaction. Our strategy could find applications in various fields such as thermal catalysis, nitration, acylation and the synthesis of other chemicals.

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Fig. 1: Comparison of conventional esterification and the designed interfacial photothermal catalysis-based esterification.
Fig. 2: Preparation and characterization of SGA as an interfacial photothermal catalytic material.
Fig. 3: Catalytic properties of SGA.
Fig. 4: In situ separation properties of reactants and products by SGA.
Fig. 5: Applications of SGA as a catalyst in various esterification processes.

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Data availability

All relevant data are included in the manuscript and Supplementary Information. The data that support the findings of this study are available from the corresponding authors upon request.

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Acknowledgements

We acknowledge the micro-fabrication centre at the National Laboratory of Solid State Microstructures (NLSSM) for technical support. This work is jointly supported by the National Key Research and Development Programme of China (numbers 2021YFA1400700, 2020YFA0406104 and 2017YFA0205700), National Natural Science Foundation of China (numbers 52002168, 12022403, 51925204, 11874211 and 61735008), Science Foundation of Jiangsu (BK20190311), Key Science and Technology Innovation Programme of Shandong Province (2019JZZY020704), Excellent Research Programme of Nanjing University (ZYJH005) and the Fundamental Research Funds for the Central Universities (numbers 021314380184, 021314380190, 021314380140 and 021314380150). J.Z. acknowledges support from the XPLORER PRIZE.

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Author notes

  1. These authors contributed equally: Pengcheng Yao, Han Gong, Zhen-Yu Wu.

Authors and Affiliations

  1. National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, Frontiers Science Center for Critical Earth Material Cycling, Nanjing University, Nanjing, P. R. China

    Pengcheng Yao, Han Gong, Hanyu Fu, Bo Li, Bin Zhu, Xueyang Wang, Ning Xu, Huigang Zhang & Jia Zhu

  2. Department of Chemical and Biomolecular Engineering, Rice University, Houston, TX, USA

    Zhen-Yu Wu

  3. School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, P. R. China

    Jiawei Ji & Changjin Tang

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  1. Pengcheng Yao
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Contributions

B.Z. and J.Z. conceived and designed the project. P.Y., H.G., Z.-Y.W., B.L. and J.J. performed the material preparation and characterizations. P.Y. and H.G. contributed to the catalysis experiments. H.F. performed the calculations. B.Z., P.Y., H.G., Z.-Y.W. and J.Z. wrote the manuscript. All the authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Bin Zhu or Jia Zhu.

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Peer review information

Nature Sustainability thanks Yu-Wen Chen, Jorge Gascon, Hai-Long Jiang, Ding Ma and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–16, Discussion and Tables 1–2.

Supplementary Video 1

Contact angle between ethanol and SGA.

Supplementary Video 2

Contact angle between acetic acid and SGA.

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Yao, P., Gong, H., Wu, ZY. et al. Greener and higher conversion of esterification via interfacial photothermal catalysis. Nat Sustain 5, 348–356 (2022). https://doi.org/10.1038/s41893-021-00841-0

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