Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Programmable heating and quenching for efficient thermochemical synthesis

Nature volume 605, pages 470–476 (2022)Cite this article

Subjects

Abstract

Conventional thermochemical syntheses by continuous heating under near-equilibrium conditions face critical challenges in improving the synthesis rate, selectivity, catalyst stability and energy efficiency, owing to the lack of temporal control over the reaction temperature and time, and thus the reaction pathways1,2,3. As an alternative, we present a non-equilibrium, continuous synthesis technique that uses pulsed heating and quenching (for example, 0.02 s on, 1.08 s off) using a programmable electric current to rapidly switch the reaction between high (for example, up to 2,400 K) and low temperatures. The rapid quenching ensures high selectivity and good catalyst stability, as well as lowers the average temperature to reduce the energy cost. Using CH4 pyrolysis as a model reaction, our programmable heating and quenching technique leads to high selectivity to value-added C2 products (>75% versus <35% by the conventional non-catalytic method and versus <60% by most conventional methods using optimized catalysts). Our technique can be extended to a range of thermochemical reactions, such as NH3 synthesis, for which we achieve a stable and high synthesis rate of about 6,000 μmol gFe−1 h−1 at ambient pressure for >100 h using a non-optimized catalyst. This study establishes a new model towards highly efficient non-equilibrium thermochemical synthesis.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Comparison between our PHQ method and conventional continuous heating using a CH4 pyrolysis model reaction.
Fig. 2: Operation of the PHQ technique.
Fig. 3: The utility and advantages of our PHQ technique.
Fig. 4: NH3 synthesis by PHQ under ambient pressure.

Similar content being viewed by others

Data availability

The data that support the findings of this study are available within this article and its Supplementary Information. Further data are available from the corresponding authors on reasonable request. Source data are provided with this paper.

Code availability

The code used for active learning has been deposited in the Code Ocean repository (ref. 41).

References

  1. Bailey, J. E. Periodic operation of chemical reactors: a review. Chem. Eng. Commun. 1, 111–124 (1973).

    Article  Google Scholar 

  2. Wolff, J., Papathanasiou, A. G., Kevrekidis, I. G., Rotermund, H. H. & Ertl, G. Spatiotemporal addressing of surface activity. Science 294, 134–137 (2001).

    Article  ADS  CAS  Google Scholar 

  3. Kevrekidis, I. G., Schmidt, L. D. & Aris, R. Some common features of periodically forced reacting systems. Chem. Eng. Sci. 41, 1263–1276 (1986).

    Article  CAS  Google Scholar 

  4. Chorkendorff, I. & Niemantsverdriet, J. W. Concepts of Modern Catalysis and Kinetics 3rd edn (Wiley, 2017).

  5. Marin, G. B., Yablonsky, G. S. & Constales, D. Kinetics of Chemical Reactions: Decoding Complexity 2nd edn (Wiley, 2019).

  6. Papathanasiou, A. G., Wolff, J., Kevrekidis, I. G., Rotermund, H. H. & Ertl, G. Some twists and turns in the path of improving surface activity. Chem. Phys. Lett. 358, 407–412 (2002).

    Article  ADS  CAS  Google Scholar 

  7. Guo, X. et al. Direct, nonoxidative conversion of methane to ethylene, aromatics, and hydrogen. Science 344, 616–619 (2014).

    Article  ADS  CAS  Google Scholar 

  8. Calkins, W. H. & Bonifaz, C. Coal flash pyrolysis: 5. Pyrolysis in an atmosphere of methane. Fuel 63, 1716–1719 (1984).

    Article  CAS  Google Scholar 

  9. Hao, J. et al. Enhanced methane conversion to olefins and aromatics by H-donor molecules under nonoxidative condition. ACS Catal. 9, 9045–9050 (2019).

    Article  CAS  Google Scholar 

  10. Sakbodin, M., Wu, Y., Oh, S. C., Wachsman, E. D. & Liu, D. Hydrogen-permeable tubular membrane reactor: promoting conversion and product selectivity for non-oxidative activation of methane over an Fe@SiO2 catalyst. Angew. Chem. Int. Ed. 55, 16149–16152 (2016).

    Article  CAS  Google Scholar 

  11. Šot, P. et al. Non-oxidative methane coupling over silica versus silica-supported iron(II) single sites. Chem. Eur. J. 26, 8012–8016 (2020).

    Article  Google Scholar 

  12. Wu, Y. et al. Overgrowth of lamellar silicalite-1 on MFI and BEA zeolites and its consequences on non-oxidative methane aromatization reaction. Microporous Mesoporous Mater. 263, 1–10 (2018).

    Article  CAS  Google Scholar 

  13. Liu, L. et al. Methane dehydroaromatization on Mo/HMCM-22 catalysts: Effect of SiO2/Al2O3 ratio of HMCM-22 zeolite supports. Catal. Lett. 108, 25–30 (2006).

    Article  CAS  Google Scholar 

  14. Zhang, Y. et al. Promotional effects of In on non-oxidative methane transformation over Mo-ZSM-5. Catal. Lett. 146, 1903–1909 (2016).

    Article  CAS  Google Scholar 

  15. Aboul-Gheit, A. K., Awadallah, A. E., Aboul-Enein, A. A. & Mahmoud, A.-L. H. Molybdenum substitution by copper or zinc in H-ZSM-5 zeolite for catalyzing the direct conversion of natural gas to petrochemicals under non-oxidative conditions. Fuel 90, 3040–3046 (2011).

    Article  CAS  Google Scholar 

  16. Bajec, D., Kostyniuk, A., Pohar, A. & Likozar, B. Micro-kinetics of non-oxidative methane coupling to ethylene over Pt/CeO2 catalyst. Chem. Eng. J. 396, 125182 (2020).

    Article  CAS  Google Scholar 

  17. Xie, P. et al. Nanoceria-supported single-atom platinum catalysts for direct methane conversion. ACS Catal. 8, 4044–4048 (2018).

    Article  CAS  Google Scholar 

  18. Xiao, Y. & Varma, A. Highly selective nonoxidative coupling of methane over Pt-Bi bimetallic catalysts. ACS Catal. 8, 2735–2740 (2018).

    Article  CAS  Google Scholar 

  19. Butland, A. T. D. & Maddison, R. J. The specific heat of graphite: an evaluation of measurements. J. Nucl. Mater. 49, 45–56 (1973).

    Article  ADS  CAS  Google Scholar 

  20. Bao, W. et al. Flexible, high temperature, planar lighting with large scale printable nanocarbon paper. Adv. Mater. 28, 4684–4691 (2016).

    Article  CAS  Google Scholar 

  21. Van Geem, K. M., Galvita, V. V. & Marin, G. B. Making chemicals with electricity. Science 364, 734–735 (2019).

    Article  ADS  Google Scholar 

  22. Wismann, S. T. et al. Electrified methane reforming: a compact approach to greener industrial hydrogen production. Science 364, 756–759 (2019).

    Article  ADS  CAS  Google Scholar 

  23. Bai, Z., Chen, H., Li, B. & Li, W. Catalytic decomposition of methane over activated carbon. J. Anal. Appl. Pyrolysis 73, 335–341 (2005).

    Article  CAS  Google Scholar 

  24. Gao, Z., Kobayashi, M., Wang, H., Onoe, K. & Yamaguchi, T. Methane conversion in thermal diffusion column reactor with carbon rod as pyrogen. Fuel Process. Technol. 88, 996–1001 (2007).

    Article  CAS  Google Scholar 

  25. Shields, B. J. et al. Bayesian reaction optimization as a tool for chemical synthesis. Nature 590, 89–96 (2021).

    Article  ADS  CAS  Google Scholar 

  26. Wang, Y., Chen, T.-Y. & Vlachos, D. NEXTorch: a design and Bayesian optimization toolkit for chemical sciences and engineering. J. Chem. Inf. Model. 61, 5312–5319 (2021).

    Article  CAS  Google Scholar 

  27. Frenklach, M. Reaction mechanism of soot formation in flames. Phys. Chem. Chem. Phys. 4, 2028–2037 (2002).

  28. Yablonsky, G. S., Constales, D. & Marin, G. B. Equilibrium relationships for non-equilibrium chemical dependencies. Chem. Eng. Sci. 66, 111–114 (2011).

    Article  CAS  Google Scholar 

  29. Silva, G. D. Mystery of 1-vinylpropargyl formation from acetylene addition to the propargyl radical: an open-and-shut case. J. Phys. Chem. A 121, 2086–2095 (2017).

    Article  Google Scholar 

  30. Mansurov, Z. A. Soot formation in combustion processes. Combust. Explos. Shock Waves 41, 727–744 (2005).

    Article  Google Scholar 

  31. Saadatjou, N., Jafari, A. & Sahebdelfar, S. Ruthenium nanocatalysts for ammonia synthesis: a review. Chem. Eng. Commun. 202, 420–448 (2015).

    Article  CAS  Google Scholar 

  32. Qin, R. et al. Alkali ions secure hydrides for catalytic hydrogenation. Nat. Catal. 3, 703–709 (2020).

    Article  CAS  Google Scholar 

  33. Dahl, S., Sehested, J., Jacobsen, C. J. H., Törnqvist, E. & Chorkendorff, I. Surface science based microkinetic analysis of ammonia synthesis over ruthenium catalysts. J. Catal. 192, 391–399 (2000).

    Article  CAS  Google Scholar 

  34. Bowker, M., Parker, I. B. & Waugh, K. C. Extrapolation of the kinetics of model ammonia synthesis catalysts to industrially relevant temperatures and pressures. Appl. Catal. 14, 101–118 (1985).

    Article  CAS  Google Scholar 

  35. Wu, L., Hu, S., Yu, W., Shen, S. & Li, T. Stabilizing mechanism of single-atom catalysts on a defective carbon surface. NPJ Comput. Mater. 6, 1–8 (2020).

    Article  ADS  Google Scholar 

  36. Özçelik, V. O., Gurel, H. H. & Ciraci, S. Self-healing of vacancy defects in single-layer graphene and silicene. Phys. Rev. B 88, 045440 (2013).

    Article  ADS  Google Scholar 

  37. Ye, T.-N. et al. Vacancy-enabled N2 activation for ammonia synthesis on an Ni-loaded catalyst. Nature 583, 391–395 (2020).

    Article  ADS  CAS  Google Scholar 

  38. Gong, Y. et al. Ternary intermetallic LaCoSi as a catalyst for N2 activation. Nat. Catal. 1, 178–185 (2018).

    Article  CAS  Google Scholar 

  39. Kitano, M. et al. Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store. Nat. Chem. 4, 934–940 (2012).

    Article  CAS  Google Scholar 

  40. Shi, M.-M. et al. Au sub-nanoclusters on TiO2 toward highly efficient and selective electrocatalyst for N2 conversion to NH3 at ambient conditions. Adv. Mater. 29, 1606550 (2017).

    Article  Google Scholar 

  41. Dong, Q. et al. Active learning for programmable heating and quenching. Code Ocean https://doi.org/10.24433/CO.1790371.v1 (2021).

Download references

Acknowledgements

We acknowledge the support from the University of Maryland A. James Clark School of Engineering. We acknowledge the Maryland NanoCenter, the Surface Analysis Center and the AIM Lab. We thank M. R. Zachariah and D. J. Kline from the University of California, Riverside for their help on the temperature measurements. We thank E. Schulman from the University of Maryland, College Park for her help on the energy cost calculations. D.L. acknowledges the support from the Department of Energy, Office of Fossil Energy (DE-FE0031877). D.G.V. acknowledges the support from the Department of Energy, Office of Energy Efficiency and Renewable Energy and Advanced Manufacturing Office (DE-EE0007888-9.5). The Delaware Energy Institute acknowledges the support and partnership of the State of Delaware in furthering the essential scientific research being conducted through the RAPID projects. Y.J. acknowledges the support from the National Science Foundation (NSF EFRI DCheM-2029425).

Author information

Author notes

  1. Konstantinos Alexopoulos

    Present address: Department of Chemical Engineering, The Pennsylvania State University, University Park, PA, USA

  2. Hilal Ezgi Toraman

    Present address: Department of Energy and Mineral Engineering, The Pennsylvania State University, University Park, PA, USA

  3. These authors contributed equally: Qi Dong, Yonggang Yao, Sichao Cheng, Konstantinos Alexopoulos

Authors and Affiliations

  1. Department of Materials Science and Engineering, University of Maryland, College Park, MD, USA

    Qi Dong, Yonggang Yao, Jinlong Gao, Alexandra H. Brozena, Xizheng Wang & Liangbing Hu

  2. Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD, USA

    Sichao Cheng & Dongxia Liu

  3. Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE, USA

    Konstantinos Alexopoulos, Sanjana Srinivas, Yifan Wang, Hilal Ezgi Toraman & Dionisios G. Vlachos

  4. Department of Mechanical Engineering, University of Maryland, College Park, MD, USA

    Yong Pei, Chaolun Zheng & Bao Yang

  5. Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ, USA

    Hao Zhao & Yiguang Ju

  6. Department of Chemical and Biomolecular Engineering, Department of Applied Mathematics and Statistics, Johns Hopkins University, Baltimore, MD, USA

    Ioannis G. Kevrekidis

  7. Center for Materials Innovation, University of Maryland, College Park, MD, USA

    Liangbing Hu

Authors
  1. Qi Dong
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yonggang Yao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Sichao Cheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Konstantinos Alexopoulos
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jinlong Gao
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Sanjana Srinivas
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Yifan Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Yong Pei
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Chaolun Zheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Alexandra H. Brozena
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Hao Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Xizheng Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Hilal Ezgi Toraman
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Bao Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Ioannis G. Kevrekidis
    View author publications

    You can also search for this author in PubMed Google Scholar

  16. Yiguang Ju
    View author publications

    You can also search for this author in PubMed Google Scholar

  17. Dionisios G. Vlachos
    View author publications

    You can also search for this author in PubMed Google Scholar

  18. Dongxia Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  19. Liangbing Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

L.H., Q.D. and Y.Y. came up with the design concept. Q.D. and S.C. designed the reactor and collected the data for CH4 pyrolysis. Q.D., Y.Y. and J.G. collected the data for NH3 synthesis. K.A., H.E.T. and D.G.V. carried out the simulation for CH4 pyrolysis and the energy cost calculation. S.S. and Y.W. conducted the active learning. Q.D. and X.W. performed the temperature measurements. Y.P., C.Z. and B.Y. carried out the modelling for the temperature profile of the gas molecules. J.G. collected the digital images. Q.D. and Y.Y. conducted the spectroscopic and microscopic analysis. K.A., D.G.V., H.Z. and Y.J. carried out the simulation for NH3 synthesis. I.G.K. helped analyse the overall results. L.H., Q.D., Y.Y. and A.H.B. collectively wrote the paper, together with input from all authors. L.H., D.L. and D.G.V. supervised the project. All authors discussed the results and contributed to the final manuscript.

Corresponding authors

Correspondence to Dionisios G. Vlachos, Dongxia Liu or Liangbing Hu.

Ethics declarations

Competing interests

L.H., Y.Y., Q.D. and D.L. report a patent application of ‘High-temperature shock heating for thermochemical reactions’ filed on 12 March 2021, US application no. PCT/US2021/022204.

Peer review

Peer review information

Nature thanks the anonymous reviewers for their contribution to the peer review of this work.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

This file contains Supplementary Methods; Supplementary Tables 1–3; Supplementary Discussions 1–15 and Supplementary References.

Source data

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Dong, Q., Yao, Y., Cheng, S. et al. Programmable heating and quenching for efficient thermochemical synthesis. Nature 605, 470–476 (2022). https://doi.org/10.1038/s41586-022-04568-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41586-022-04568-6

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing