MOF-Triggered Synthesis of Subnanometer Ag02 Clusters and Fe3+ Single Atoms: Heterogenization Led to Efficient and Synergetic One-Pot Catalytic Reactions
Journal of the American Chemical Society， Pub Date : 2023-04-28 ,
DOI: 10.1021/jacs.3c02155
Estefanía Tiburcio, Yongkun Zheng, Cristina Bilanin, Juan Carlos Hernández-Garrido, Alejandro Vidal-Moya, Judit Oliver-Meseguer, Nuria Martín, Marta Mon, Jesús Ferrando-Soria, Donatella Armentano, Antonio Leyva-Pérez, Emilio Pardo
The combination of well-defined Fe3+ isolated single-metal atoms and Ag2 subnanometer metal clusters within the channels of a metal–organic framework (MOF) is reported and characterized by single-crystal X-ray diffraction for the first time. The resulting hybrid material, with the formula [Ag02(Ag0)1.34FeIII0.66]@NaI2{NiII4[CuII2(Me3mpba)2]3}·63H2O (Fe3+Ag02@MOF), is capable of catalyzing the unprecedented direct conversion of styrene to phenylacetylene in one pot. In particular, Fe3+Ag02@MOF─which can easily be obtained in a gram scale─exhibits superior catalytic activity for the TEMPO-free oxidative cross-coupling of styrenes with phenyl sulfone to give vinyl sulfones in yields up to >99%, which are ultimately transformed, in situ, to the corresponding phenylacetylene product. The results presented here constitute a paradigmatic example of how the synthesis of different metal species in well-defined solid catalysts, combined with speciation of the true metal catalyst of an organic reaction in solution, allows the design of a new challenging reaction.
https://pubs.acs.org/doi/full/10.1021/jacs.3c02155
Solvent-derived defects suppress adsorption in MOF-74
Nature Communications ， Pub Date : 2023-04-25 ,
DOI: 10.1038/s41467-023-38155-8
Yao Fu, Yifeng Yao, Alexander C. Forse, Jianhua Li, Kenji Mochizuki, Jeffrey R. Long, Jeffrey A. Reimer, Gaël De Paëpe, Xueqian Kong
Defects in metal-organic frameworks (MOFs) have great impact on their nano-scale structure and physiochemical properties. However, isolated defects are easily concealed when the frameworks are interrogated by typical characterization methods. In this work, we unveil the presence of solvent-derived formate defects in MOF-74, an important class of MOFs with open metal sites. With multi-dimensional solid-state nuclear magnetic resonance (NMR) investigations, we uncover the ligand substitution role of formate and its chemical origin from decomposed N,N-dimethylformamide (DMF) solvent. The placement and coordination structure of formate defects are determined by 13C NMR and density functional theory (DFT) calculations. The extra metal-oxygen bonds with formates partially eliminate open metal sites and lead to a quantitative decrease of N2 and CO2 adsorption with respect to the defect concentration. In-situ NMR analysis and molecular simulations of CO2 dynamics elaborate the adsorption mechanisms in defective MOF-74. Our study establishes comprehensive strategies to search, elucidate and manipulate defects in MOFs.
https://www.nature.com/articles/s41467-023-38155-8
Photo-Enhanced Chemo-Transistor Platform for Ultrasensitive Assay of Small Molecules
Journal of the American Chemical Society，Pub Date : 2023-04-25 ,
DOI: 10.1021/jacs.2c13655
Qiankun Wang, Zhaolin Ai, Qianying Guo, Xuejun Wang, Changhao Dai, Hancheng Wang, Jiang Sun, Yanan Tang, Dingding Jiang, Xinjie Pei, Renzhong Chen, Jian Gou, Lin Yu, Jiandong Ding, Andrew T. S. Wee, Yunqi Liu, and Dacheng Wei*
Compared with traditional assay techniques, field-effect transistors (FETs) have advantages such as fast response, high sensitivity, being label-free, and point-of-care detection, while lacking generality to detect a wide range of small molecules since most of them are electrically neutral with a weak doping effect. Here, we demonstrate a photo-enhanced chemo-transistor platform based on a synergistic photo-chemical gating effect in order to overcome the aforementioned limitation. Under light irradiation, accumulated photoelectrons generated from covalent organic frameworks offer a photo-gating modulation, amplifying the response to small molecule adsorption including methylglyoxal, p-nitroaniline, nitrobenzene, aniline, and glyoxal when measuring the photocurrent. We perform testing in buffer, artificial urine, sweat, saliva, and diabetic mouse serum. The limit of detection is down to 10–19 M methylglyoxal, about 5 orders of magnitude lower than existing assay technologies. This work develops a photo-enhanced FET platform to detect small molecules or other neutral species with enhanced sensitivity for applications in fields such as biochemical research, health monitoring, and disease diagnosis.
Raman spectroscopy, an ideal tool for studying the physical properties and applications of metal–organic frameworks (MOFs)
Chemical Society Reviews ， Pub Date : 2023-04-24 ,
DOI: 10.1039/d2cs01004f
Janaky Sunil, Chandrabhas Narayana, Gayatri Kumari , Kolleboyina Jayaramulu