PMID- 31433625
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20190904
IS  - 1520-510X (Electronic)
IS  - 0020-1669 (Linking)
VI  - 58
IP  - 17
DP  - 2019 Sep 3
TI  - Adenine-Based Zn(II)/Cd(II) Metal-Organic Frameworks as Efficient Heterogeneous 
      Catalysts for Facile CO(2) Fixation into Cyclic Carbonates: A DFT-Supported Study 
      of the Reaction Mechanism.
PG  - 11389-11403
LID - 10.1021/acs.inorgchem.9b00814 [doi]
AB  - We synthesized two new adenine-based Zn(II)/Cd(II) metal-organic frameworks 
      (MOFs), namely, [Zn(2)(H(2)O)(stdb)(2)(5H-Ade)(9H-Ade)(2)](n) (PNU-21) and 
      [Cd(2)(Hstdb)(stdb)(8H-Ade)(Ade)](n) (PNU-22), containing auxiliary dicarboxylate 
      ligand (stdb = 4,4'-stilbenedicarboxylate). Both MOFs were characterized by 
      multiple analytical techniques such as single-crystal X-ray diffraction (SXRD), 
      powder X-ray diffraction, Fourier transform infrared spectroscopy, X-ray 
      photoelectron spectroscopy, thermogravimetric analysis, scanning electron 
      microscopy, as well as temperature program desorption and Brunauer-Emmett-Teller 
      measurements. Both MOFs were structurally robust and possessed unsaturated Lewis 
      acidic metal centers [Zn(II) and Cd(II)] and free basic N atoms of adenine 
      molecules. They were used as heterogeneous catalysts for the fixation of CO(2) 
      into five-membered cyclic carbonates. Significant conversion of epichlorohydrin 
      (ECH) was attained at a low CO(2) pressure (0.4 MPa) and moderate catalyst (0.6 
      mol %)/cocatalyst (0.3 mol %) amounts, with over 99% selectivity toward the ECH 
      carbonate. They showed comparable or even higher catalytic activity than other 
      previously reported MOFs. Because of high thermal stability and robust 
      architecture of PNU-21/PNU-22, both catalysts could be reused with simple 
      separation up to five successive cycles without any considerable loss of their 
      catalytic activity. Densely populated acidic and basic sites in both 
      Zn(II)/Cd(II) MOFs facilitated the conversion of ECH to ECH carbonate in high 
      yields. The reaction mechanism of the cycloaddition reaction between ECH and 
      CO(2) is described by possible intermediates, transition states, and pathways, 
      from the density functional theory calculation in correlation with the SXRD 
      structure of PNU-21.
FAU - Rachuri, Yadagiri
AU  - Rachuri Y
AUID- ORCID: 0000-0003-2979-2876
FAU - Kurisingal, Jintu Francis
AU  - Kurisingal JF
FAU - Chitumalla, Ramesh Kumar
AU  - Chitumalla RK
AUID- ORCID: 0000-0002-9523-7056
FAU - Vuppala, Srimai
AU  - Vuppala S
FAU - Gu, Yunjang
AU  - Gu Y
FAU - Jang, Joonkyung
AU  - Jang J
AUID- ORCID: 0000-0001-9028-0605
FAU - Choe, Youngson
AU  - Choe Y
AUID- ORCID: 0000-0001-9536-113X
FAU - Suresh, Eringathodi
AU  - Suresh E
AUID- ORCID: 0000-0002-1934-6832
AD  - Analytical and Environmental Science Division and Centralized Instrument Facility 
      , Central Salt and Marine Chemicals Research Institute , G. B. Marg , Bhavnagar 
      364 002 , India.
FAU - Park, Dae-Won
AU  - Park DW
AUID- ORCID: 0000-0003-4668-4906
LA  - eng
PT  - Journal Article
DEP - 20190821
PL  - United States
TA  - Inorg Chem
JT  - Inorganic chemistry
JID - 0366543
SB  - IM
EDAT- 2019/08/23 06:00
MHDA- 2019/08/23 06:01
CRDT- 2019/08/22 06:00
PHST- 2019/08/23 06:00 [pubmed]
PHST- 2019/08/23 06:01 [medline]
PHST- 2019/08/22 06:00 [entrez]
AID - 10.1021/acs.inorgchem.9b00814 [doi]
PST - ppublish
SO  - Inorg Chem. 2019 Sep 3;58(17):11389-11403. doi: 10.1021/acs.inorgchem.9b00814. 
      Epub 2019 Aug 21.