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Structure elucidation of a complex CO2-based organic framework material by NMR crystallography.

ABSTRACT: A three-dimensional structural model of a complex CO2-based organic framework made from high molecular weight, self-assembled, flexible and multi-functional oligomeric constituents has been determined de novo by solid-state NMR including DNP-enhanced experiments. The complete assignment of the 15N, 13C and 1H resonances was obtained from a series of two-dimensional through space and through bond correlation experiments. MM-QM calculations were used to generate different model structures for the material which were then evaluated by comparing multiple experimental and calculated NMR parameters. Both NMR and powder X-ray diffraction were evaluated as tools to determine the packing by crystal modelling, and at the level of structural modelling used here PXRD was found not to be a useful complement. The structure determined reveals a highly optimised H-bonding network that explains the unusual selectivity of the self-assembly process which generates the material. The NMR crystallography approach used here should be applicable for the structure determination of other complex solid materials.

SUBMITTER: Leclaire J

PROVIDER: S-EPMC6014084 | biostudies-other | 2016 Jul

REPOSITORIES: biostudies-other

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Structure elucidation of a complex CO2-based organic framework material by NMR crystallography.

Leclaire Julien J Poisson Guillaume G Ziarelli Fabio F Pepe Gerard G Fotiadu Frédéric F Paruzzo Federico M FM Rossini Aaron J AJ Dumez Jean-Nicolas JN Elena-Herrmann Bénédicte B Emsley Lyndon L

Chemical science 20160322 7

A three-dimensional structural model of a complex CO2-based organic framework made from high molecular weight, self-assembled, flexible and multi-functional oligomeric constituents has been determined de novo by solid-state NMR including DNP-enhanced experiments. The complete assignment of the 15N, 13C and 1H resonances was obtained from a series of two-dimensional through space and through bond correlation experiments. MM-QM calculations were u ...[more]

PMID: 30155085

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Project description:Metal-organic frameworks (MOFs) have been an excellent platform for carbon dioxide reduction reactions (CO2RR). In this work, the feasibility of electrochemical reduction of CO2 to obtain C2-deep value-added products was investigated by the preparation of Mg-containing MOF-74 samples combined with transition metal cations (Ni2+, Co2+ and Zn2+). The prepared MOFs were used as electrocatalysts in CO2RR. Chronoamperometric analysis coupled to ATR-FTIR spectroscopy was employed to characterize the CO2 reduction products and subsequently via 1H NMR. Although an isostructural crystalline structure was observed in all synthesized MOFs, the pore diameter distribution was significantly affected due to the Mg coordination along with each transition metal nuclei with the organic ligand to form the MOF-74. Our results showed that Mg-containing MOF-74 electrocatalysts combined with Ni, Co and Zn ions successfully reduced CO2 to C2-deep products, while the monometallic Mg-MOF-74 showed only CO2 mineralization. An ester acetate, isopropyl alcohol, and formic acid were produced by Mg/Ni-MOF-74; isopropyl alcohol was provided by Mg/Co-MOF-74, and ethanol was generated by Mg/Zn-MOF-74. We observed that the change of the transition cation was a key factor in the selectivity of the obtained products, while the degree of Mg ions effectively incorporated into the MOF structure tuned the porosity and the electrocatalytic activity. Among them, Mg/Zn-MFOF-74 showed the highest Mg content loaded after synthesis and thus the most favorable electrocatalytic behavior towards CO2 reduction. Highlights • CO2-derived C2-deep reduction products were obtained by Mg-containing MOF-74 bimetallic electrocatalysts.• Mg-containing MOF-74 bimetallic electrocatalysts reduced CO2 to ester acetate, isopropanol, formic acid, and ethanol.• Mg/Zn-MOF-74 displayed the highest current density at a lower onset potential in CO2-saturated electrolyte.• The pore network could be tuned by the effective Mg content on a MOF-74 bimetallic sample.• Mg/Zn-MOF-74 showed the highest Mg content among all bimetallic electrocatalysts after the synthesis.

Dataset Information

Structure elucidation of a complex CO2-based organic framework material by NMR crystallography.

Publications

Structure elucidation of a complex CO<sub>2</sub>-based organic framework material by NMR crystallography.

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