Beyond the Thermal Equilibrium Limit of Ammonia Synthesis with Dual Temperature Zone Catalyst Powered by Solar Light
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Summary Artificial ammonia synthesis (Haber-Bosch process) is a prototypical exothermic reaction of maximum catalytic yield restricted by the unbreakable equilibrium law. This is because bottlenecked N2 dissociation necessitates high temperature, but high temperature reversely shifts the thermal equilibrium toward NH3 decomposition. To surmount this equilibrium limit, here, we propose a new scenario of dual-temperature-zone catalysis. Powered by sunlight, the apparent temperature of TiO2-xHy/Fe hybrid reaches 495°C but with local temperature difference up to 137°C between the hot zone (Fe) and “cooling” zone (TiO2-xHy) owing to the plasmonic local heating effect. The hot Fe bearing hot carriers efficiently dissociates N2, while working-in-tandem TiO2-xHy well accommodates spilled-over N from Fe via successive hydrogenation, prominently mitigating the reverse equilibrium shift and thus delivering record NH3 concentrations of 1,939 (1 atm) and 19,620 ppm (10 atm) at 495°C, 1.55 and 1.57 times the theoretical equilibrium limits of 1,249 and 12,459 ppm, respectively.
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- Authors
- Mao, C., Li, H., Gu, H., Wang, J., Zou, Y., Qi, G., Xu, J., Deng, F., Shen, W., Li, J., Liu, S., Zhao, J., & Zhang, L.
- Affiliations
- Central China Normal University (CN)
- State Key Laboratory of Digital Manufacturing Equipment and Technology (CN)
- Chinese Academy of Sciences (CN)
- Corresponding author
- Zhang, Lizhi
- ORCID
- Venue
- Chem
- Publisher
- Elsevier BV
- Published
- 2019-10
- Volume
- 5
- Issue
- 10
- Pages
- 2702-2717
- ISSN
- 2451-9294 (ISSN-L)
- OpenAlex
- W2969516292
- Cited by
- 180
- References
- 72
- Citations by year
- 2026: 26 · 2025: 30 · 2024: 38 · 2023: 23 · 2022: 21 · 2021: 30 · 2020: 11 · 2019: 1
- FWCI
- 3.22
- Type
- journal article
- Language
- en
- Open access
- bronze
- doi.org
- Licence
- Locations
- Chem (publishedVersion)
- Funders
- Zhejiang University of Technology (10,112,841)
- National Key Research and Development Program of China (2016YFA0203002)
- National Science Fund for Distinguished Young Scholars (21425728)
- National Natural Science Foundation of China (21872061, 51472100, 51727809, 51805193)
- Central China Normal University (2018YBZZ024)
- Tongji University
- Topics
- Physical Sciences › Chemical Engineering › Catalysis › Ammonia Synthesis and Nitrogen Reduction
- Physical Sciences › Engineering › Biomedical Engineering › Chemical Looping and Thermochemical Processes
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Advanced Photocatalysis Techniques
- Keywords
- ammonia synthesis, Haber-Bosch process, solar photocatalysis, nitrogen dissociation, hot carrier transfer, hydrogenation, tandem catalysis
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