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Vol. 17 (2025)

Design of Ultra-Stable Solid Amine Adsorbents and Mechanisms of Hydroxyl Group-Dependent Deactivation for Reversible CO2 Capture from Flue Gas

https://doi.org/10.1007/s40820-025-01664-w
Meng Zhao
College of Environmental Science and Engineering, Beijing Forestry University, Beijing 100083, People’s Republic of China
Liang Huang
College of Environmental Science and Engineering, Beijing Forestry University, Beijing 100083, People’s Republic of China
Yanshan Gao
College of Environmental Science and Engineering, Beijing Forestry University, Beijing 100083, People’s Republic of China
Ziling Wang
College of Environmental Science and Engineering, Beijing Forestry University, Beijing 100083, People’s Republic of China
Shuyu Liang
College of Environmental Science and Engineering, Beijing Forestry University, Beijing 100083, People’s Republic of China
Xuancan Zhu
Research Center of Solar Power and Refrigeration, Institute of Refrigeration and Cryogenics, Shanghai Jiao Tong University, Shanghai 200240, People’s Republic of China
Qiang Wang
College of Environmental Science and Engineering, Beijing Forestry University, Beijing 100083, People’s Republic of China
Hong He
State Key Joint Laboratory of Environment Simulation and Pollution Control, Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, People’s Republic of China
Dermot O’Hare
Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Mansfield Road, Oxford OX1 3TA, UK

Corresponding Author: Dermot O’Hare

dermot.ohare@chem.ox.ac.uk

Nano-Micro Letters, Vol. 17 (2025), Article Number: 170

Abstract

Although supported solid amine adsorbents have attracted great attention for CO2 capture, critical chemical deactivation problems including oxidative degradation and urea formation have severely restricted their practical applications for flue gas CO2 capture. In this work, we reveal that the nature of surface hydroxyl groups (metal hydroxyl Al–OH and nonmetal hydroxyl Si–OH) plays a key role in the deactivation mechanisms. The polyethyleneimine (PEI) supported on Al–OH-containing substrates suffers from severe oxidative degradation during the CO2 capture step due to the breakage of amine-support hydrogen bonding networks, but exhibits an excellent anti-urea formation feature by preventing dehydration of carbamate products under a pure CO2 regeneration atmosphere. In contrast, PEI supported on Si–OH-containing substrates exhibits excellent anti-oxidative stability under simulated flue gas conditions by forming a robust hydrogen bonding protective network with Si–OH, but suffers from obvious urea formation during the pure CO2 regeneration step. We also reveal that the urea formation problem for PEI-SBA-15 can be avoided by the incorporation of an OH-containing PEG additive. Based on the intrinsic understanding of degradation mechanisms, we successfully synthesized an adsorbent 40PEI-20PEG-SBA-15 that demonstrates outstanding stability and retention of a high CO2 capacity of 2.45 mmol g−1 over 1000 adsorption–desorption cycles, together with negligible capacity loss during aging in simulated flue gas (10% CO2 + 5% O2 + 3% H2O) for one month at 60–70 °C. We believe this work makes great contribution to the advancement in the field of ultra-stable solid amine-based CO2 capture materials.


Highlights:
1 We reveal that the nature of the hydrogen bonding networks formed by surface hydroxyl groups plays a key role in the deactivation mechanisms of supported polyethylenimine (PEI), which exhibits contrasting oxidative and anti-urea properties when supported on Al–OH- and Si–OH-containing substrates.
2 PEG modification helps reduce urea formation for PEI supported on Si–OH-containing substrates, but does not prevent oxidation of the Al–OH-containing support. The resulted ultra-stable 40PEI-20PEG-SBA-15 showing outstanding stability over 1000 adsorption–desorption cycles (2.45 mmol g−1) and negligible capacity loss after one month in simulated flue gas.

Keywords

CO2 capture Solid amine adsorbent Long-term stability Oxidative degradation Urea formation
Zhao, Meng, Liang Huang, Yanshan Gao, Ziling Wang, Shuyu Liang, Xuancan Zhu, Qiang Wang, Hong He, and Dermot O’Hare. 2025. “Design of Ultra-Stable Solid Amine Adsorbents and Mechanisms of Hydroxyl Group-Dependent Deactivation for Reversible CO2 Capture from Flue Gas”. Nano-Micro Letters 17 (February):170. https://doi.org/10.1007/s40820-025-01664-w.
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