Engineering Metal Pyrazolate Coordination Polymers for Highly Selective Direct Air Capture via Metal-Ligand Cooperativity and Moisture-Gated Mechanism.
6 affiliations
- 1Institute of Biomedical Engineering, National Tsing Hua University, Hsinchu300044, Taiwan.
- 2Department of Chemistry, National Tsing Hua University, Hsinchu300044, Taiwan.
- 3Department of Chemical Engineering, National Tsing Hua University, Hsinchu300044, Taiwan.
- 4Institute of Environmental Engineering, National Yang Ming Chiao Tung University, Hsinchu300093, Taiwan.
- 5National Synchrotron Radiation Research Center , Hsinchu30076, Taiwan.
- 6Department of Chemistry, Chung Yuan Christian University, Taoyuan320314, Taiwan.
Abstract
Direct air capture (DAC) of CO2 has emerged as an indispensable negative emission technology, yet current sorbents remain constrained by the persistent trade-off between intrinsic capture capacity and regeneration energy alongside the extrinsic challenge of atmospheric moisture inhibition. Herein, engineering of crystalline and thermally stable alkali metal pyrazolate coordination polymers (MRPyr) is established as a novel paradigm for the metal-ligand cooperative (MLC), moisture-gated, and highly selective capture of CO2 from ambient air streams. While inert in low-humidity air, activation of solid-state MRPyr by atmospheric moisture unlocks exceptional CO2-capture capacities (7.4-9.2 mmol/g) and realizes a substantial CO2:pyrazolate stoichiometry (0.83-0.89) through formation of metal carbamate (MRCarbamate). To elucidate the operative mechanism, crystallographic snapshots and in/ex situ spectroscopic analyses unveil that MLC hydration of KMePyr yielding KMePyr·H2O triggers a substantial structural rearrangement from a compact double-ladder chain into an expanded zig-zag architecture. This moisture-gated transformation relieves steric shielding and unleashes intrinsic nucleophilicity of pyrazolate ligands to initiate CO2 capture via a thermodynamically favored displacement of bound water. Finally, quantitative regeneration of MRPyr from CO2-saturated MRCarbamate adducts and demonstrated multiple-cycle recyclability under a temperature-vacuum swing adsorption process position the robust MRPyr platform as a paradigm-shifting class of sorbents for sustainable DAC applications.
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BibTeX
@article{yu2026engineering,
title = {{Engineering Metal Pyrazolate Coordination Polymers for Highly Selective Direct Air Capture via Metal-Ligand Cooperativity and Moisture-Gated Mechanism.}},
author = {Tsu-Chieh Yu and Chun-Kai Huang and Ru-Yun Yang and Yi-Tsung Lai and Qing-Hui Lin and Ming-Jun Han and Swatilekha Pratihar and Sue-Min Chang and Yu-Chen Chung and Bo-Hao Chen and Yu-Chun Chuang and Chia-Her Lin and Ho-Hsiu Chou and Tsai-Te Lu},
journal = {Journal of the American Chemical Society},
year = {2026},
month = oct,
doi = {10.1021/jacs.6c15929},
url = {https://europepmc.org/article/MED/42913593},
note = {CC BY},
}
RIS
TY - JOUR
TI - Engineering Metal Pyrazolate Coordination Polymers for Highly Selective Direct Air Capture via Metal-Ligand Cooperativity and Moisture-Gated Mechanism.
AU - Tsu-Chieh Yu
AU - Chun-Kai Huang
AU - Ru-Yun Yang
AU - Yi-Tsung Lai
AU - Qing-Hui Lin
AU - Ming-Jun Han
AU - Swatilekha Pratihar
AU - Sue-Min Chang
AU - Yu-Chen Chung
AU - Bo-Hao Chen
AU - Yu-Chun Chuang
AU - Chia-Her Lin
AU - Ho-Hsiu Chou
AU - Tsai-Te Lu
PY - 2026
DA - 2026/10/01
JO - Journal of the American Chemical Society
DO - 10.1021/jacs.6c15929
UR - https://europepmc.org/article/MED/42913593
AB - Direct air capture (DAC) of CO2 has emerged as an indispensable negative emission technology, yet current sorbents remain constrained by the persistent trade-off between intrinsic capture capacity and regeneration energy alongside the extrinsic challenge of atmospheric moisture inhibition. Herein, engineering of crystalline and thermally stable alkali metal pyrazolate coordination polymers (MRPyr) is established as a novel paradigm for the metal-ligand cooperative (MLC), moisture-gated, and highly selective capture of CO2 from ambient air streams. While inert in low-humidity air, activation of solid-state MRPyr by atmospheric moisture unlocks exceptional CO2-capture capacities (7.4-9.2 mmol/g) and realizes a substantial CO2:pyrazolate stoichiometry (0.83-0.89) through formation of metal carbamate (MRCarbamate). To elucidate the operative mechanism, crystallographic snapshots and in/ex situ spectroscopic analyses unveil that MLC hydration of KMePyr yielding KMePyr·H2O triggers a substantial structural rearrangement from a compact double-ladder chain into an expanded zig-zag architecture. This moisture-gated transformation relieves steric shielding and unleashes intrinsic nucleophilicity of pyrazolate ligands to initiate CO2 capture via a thermodynamically favored displacement of bound water. Finally, quantitative regeneration of MRPyr from CO2-saturated MRCarbamate adducts and demonstrated multiple-cycle recyclability under a temperature-vacuum swing adsorption process position the robust MRPyr platform as a paradigm-shifting class of sorbents for sustainable DAC applications.
SN - 0002-7863
SN - 1520-5126
ER -