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oai:figshare.com:article/34025320 2026-09-29T17:11:36Z category_1 category_4 category_915 category_7 category_8 category_14 category_24 category_873 category_39 category_734 category_135 portal_63 item_type_6 month_year_09_2026

Proton-Mediated Host–Guest Interactions Direct Nucleation and Morphology Evolution in Molecular Sieve Crystallization Daoning Wu (9627628) Sicong Ma (1391395) Lixin Liang (6112520) Yury G. Kolyagin (2566531) Yankai Bian (25138123) Tongyao Wang (4991432) Quanzheng Deng (8960600) Lu Han (151620) Olivier Lafon (1332801) Jean-Paul Amoureux (1332795) Guangjin Hou (1427449) Weili Dai (1470364) Biophysics Biochemistry Physical Sciences not elsewhere classified Medicine Microbiology Molecular Biology Evolutionary Biology Chemical Sciences not elsewhere classified Ecology Biological Sciences not elsewhere classified Computational Biology thermodynamic driving force significant mechanistic departure passive reaction medium ordered nuclei via findings redefine acidity established alkaline routes engineering molecular sieves al hmqc spectra – al condensation steering crystal morphology protons actively gate h –< sup density functional theory channel gating mechanism zeolite crystallization pathways molecular sieve crystallization acidic conditions represents >) molecular sieves 27 </ sup 1 </ sup acidic conditions protons lower p – morphology evolution dynamic gating n </ state nmr simultaneously increasing sapo -< rational basis operando nmr nucleation theory nanoscale sheet mediated dual kinetic barrier framework topologies framework assembly driven templating driven hydrolysis designable parameter controlled morphologies amorphous precursors alternating dominance aei ). active director acquiring high The crystallization of aluminophosphate (AlPO₄-<i>n</i>) and silicoaluminophosphate (SAPO-<i>n</i>) molecular sieves under acidic conditions represents a significant mechanistic departure from well-established alkaline routes for zeolites. Here, we elucidate how protons actively gate the nucleation and growth of AlPO₄-<i>n</i> /SAPO-<i>n</i> frameworks. By integrating ultrafast operando two-dimensional (2D) solid-state NMR (acquiring high-quality ¹H–²⁷Al HMQC spectra in just 30 seconds) with density functional theory (DFT) simulations, we resolve a proton-mediated dual-channel gating mechanism: under acidic conditions, protons lower the kinetic barrier for P–O–Al condensation from 0.63 to 0.25 eV while simultaneously increasing the thermodynamic driving force for framework assembly, thereby markedly accelerating nucleation. Operando NMR further reveals an alternating dominance between water/hydroxyl-driven hydrolysis and OSDA-driven templating, a dynamic gating that directs the conversion of amorphous precursors into ordered nuclei via a reversibly formed interfacial intermediate. Moreover, the protonation effect enables selective facet stabilization by acetate species, steering crystal morphology from cubic to nanoscale sheet-like or rod-like architectures across diverse topologies (AFI, CHA, AEI). Our findings redefine acidity from a passive reaction medium into an active director of zeolite crystallization pathways, establishing it as a designable parameter in nucleation theory and providing a rational basis for engineering molecular sieves with controlled morphologies and framework topologies. 2026-09-29T00:00:00Z Text Journal contribution 10.1021/jacs.6c12306.s001 https://figshare.com/articles/journal_contribution/Proton-Mediated_Host_Guest_Interactions_Direct_Nucleation_and_Morphology_Evolution_in_Molecular_Sieve_Crystallization/34025320 CC BY-NC 4.0