Solvent-derived defects suppress adsorption in MOF-74

Yao Fu; Yifeng Yao; Alexander C Forse; Jianhua Li; Kenji Mochizuki; Jeffrey R Long; Jeffrey A Reimer; Gaël De Paëpe; Xueqian Kong

doi:10.1038/s41467-023-38155-8

Solvent-derived defects suppress adsorption in MOF-74

Nat Commun. 2023 Apr 25;14(1):2386. doi: 10.1038/s41467-023-38155-8.

Authors

Yao Fu^{1

2

3

4}, Yifeng Yao², Alexander C Forse^{4

5

6}, Jianhua Li¹, Kenji Mochizuki², Jeffrey R Long^{4

6

7}, Jeffrey A Reimer⁴, Gaël De Paëpe³, Xueqian Kong^{8

9

10}

Affiliations

¹ Department of Physical Medicine and Rehabilitation, Sir Run Run Shaw Hospital, Zhejiang University, Hangzhou, 310027, PR China.
² Key Laboratory of Excited-State Materials of Zhejiang Province, Department of Chemistry, Zhejiang University, Hangzhou, 310027, PR China.
³ Univ. Grenoble Alpes, CEA, IRIG-MEM, Grenoble, France.
⁴ Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA, 94720, USA.
⁵ Department of Chemistry, University of Cambridge, Cambridge, CB2 1EW, UK.
⁶ Department of Chemistry, University of California, Berkeley, CA, 94720, USA.
⁷ Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
⁸ Department of Physical Medicine and Rehabilitation, Sir Run Run Shaw Hospital, Zhejiang University, Hangzhou, 310027, PR China. kxq@zju.edu.cn.
⁹ Key Laboratory of Excited-State Materials of Zhejiang Province, Department of Chemistry, Zhejiang University, Hangzhou, 310027, PR China. kxq@zju.edu.cn.
¹⁰ Institute of Translational Medicine, Shanghai Jiao Tong University, Shanghai, 200240, China. kxq@zju.edu.cn.

Abstract

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.

Abstract

Grants and funding