Synthesis of Leaching-Proof Single-Site Catalysts Based on Metallolinker MOFs
Abstract
The creation of single-site catalysts, for which all active sites have the same structure, is a key goal in contemporary heterogeneous catalysis. Many MOF linkers present well-defined binding sites for transition metals and may thus provide access to single-site catalysts. Depending on how the metal is introduced into the linker-based binding site, however, additional undesired species such as pore-confined nanoparticles or node-bound metal centers may be formed that can be difficult to locate. Here, we introduce catalytic interrogation as a diagnostic workflow for identifying the types of active sites that contribute to the catalytic activity observed for MOF catalysts. Using a suite of MOFs with porphyrin linkers as a case study, we combine catalytic interrogation with extensive electron microscopy to shed light on the rhodium-based active sites present in the MOF. We show that for strongly coordinating binding sites that furnish leaching-proof MOF-based catalysts, post-synthetic metalation carries a significant risk of undesired nanoparticle incorporation. MOF assembly from metalated linkers, on the other hand, generates MOFs that behave as single-site catalysts.
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BibTeX
@misc{deng2026synthesis,
title = {{Synthesis of Leaching-Proof Single-Site Catalysts Based on Metallolinker MOFs}},
author = {Hao Deng and Zihang Qiu and Alin B. Schöne and Walid Hetaba and Constanze Nicole Neumann},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010749/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010749/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Synthesis of Leaching-Proof Single-Site Catalysts Based on Metallolinker MOFs
AU - Hao Deng
AU - Zihang Qiu
AU - Alin B. Schöne
AU - Walid Hetaba
AU - Constanze Nicole Neumann
PY - 2026
DA - 2026/10/21
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010749/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010749/v1
AB - The creation of single-site catalysts, for which all active sites have the same structure, is a key goal in contemporary heterogeneous catalysis. Many MOF linkers present well-defined binding sites for transition metals and may thus provide access to single-site catalysts. Depending on how the metal is introduced into the linker-based binding site, however, additional undesired species such as pore-confined nanoparticles or node-bound metal centers may be formed that can be difficult to locate. Here, we introduce catalytic interrogation as a diagnostic workflow for identifying the types of active sites that contribute to the catalytic activity observed for MOF catalysts. Using a suite of MOFs with porphyrin linkers as a case study, we combine catalytic interrogation with extensive electron microscopy to shed light on the rhodium-based active sites present in the MOF. We show that for strongly coordinating binding sites that furnish leaching-proof MOF-based catalysts, post-synthetic metalation carries a significant risk of undesired nanoparticle incorporation. MOF assembly from metalated linkers, on the other hand, generates MOFs that behave as single-site catalysts.
ER -