Photochemical CO 2 Reduction by a Postsynthetically Modified Zr-MOF

Reji, Rosmi [Univ. of Illinois, Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)]; Vizuet, Juan P. [Univ. of Illinois, Chicago, IL (United States)] (ORCID:0000000236602041); Yan, Xiaoli [Univ. of Illinois, Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000265122338); Behera, Biki K. [Univ. of Illinois, Chicago, IL (United States)]; Zheng, Xin [Univ. of Illinois, Chicago, IL (United States)] (ORCID:0000000255068112); Klenk, Matthew [Argonne National Laboratory (ANL), Argonne, IL (United States)]; Weingartz, Nicholas P. [Northwestern Univ., Evanston, IL (United States)]; Kostopoulos, George T. [Univ. of Illinois, Chicago, IL (United States)]; Chen, Lin X. [Argonne National Laboratory (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)] (ORCID:0000000284506687); Zapol, Peter [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000305709169); Agarwal, Neeraj [Univ. of Mumbai (India)] (ORCID:0000000328532730); Huerta, Eliu [Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of Chicago, IL (United States)] (ORCID:0000000296823604); Keceli, Murat [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000185889272); Chaudhuri, Santanu [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000243282947); Glusac, Ksenija D. [Univ. of Illinois, Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:000000022734057X)

doi:10.1021/acs.inorgchem.5c02600

DOE OSTI · 3374391

Photochemical CO 2 Reduction by a Postsynthetically Modified Zr-MOF

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Abstract

Metal–organic frameworks are an excellent platform for photochemical CO 2 reduction into valuable chemicals. Herein, we report the synthesis and photocatalytic behavior of Ru@MOF-808, a Zr-based MOF, modified with a Ru-polypyridyl complex. The postsynthetic modification was achieved using solvent-assisted incorporation of bipyridine–carboxylate ligands onto the nodes of the MOF-808, followed by the coordination of Ru(II)-terpyridine moiety. A thorough characterization including 1 H NMR, diffuse reflectance UV/vis, X-ray absorption spectroscopy and gas adsorption studies, combined with DFT calculations, provides strong support for efficient incorporation of the molecular Ru-complex at the loading of one Ru center per node. In the presence of a strong sacrificial reductant BIH, Ru@MOF-808 was found to catalyze the photochemical reduction of CO 2 into a mixture of CO and formate ion. When compared to the homogeneous model catalyst Ru(tpy)(bpy) 2+ , Ru@MOF-808 was found to exhibit higher formate yields. Additionally, to explain these formate enhancements, we propose a mechanism that involves CO 2 capture at the MOF nodes to form Zr-bicarbonate species, which further react in a hydride transfer reaction with photogenerated Ru–H donor, thereby outperforming molecular catalysts in HCOO – production. Overall, the results presented in this work indicate the potential of Zr-based MOFs in integrating CO 2 capture with its photochemical conversion to desired products.

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CO2 reduction Metal-organic framework Photocatalysis Post-synthetic modification Product selectivity

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Reji, Rosmi [Univ. of Illinois, Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)], Vizuet, Juan P. [Univ. of Illinois, Chicago, IL (United States)] (ORCID:0000000236602041), Yan, Xiaoli [Univ. of Illinois, Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000265122338), Behera, Biki K. [Univ. of Illinois, Chicago, IL (United States)], Zheng, Xin [Univ. of Illinois, Chicago, IL (United States)] (ORCID:0000000255068112), Klenk, Matthew [Argonne National Laboratory (ANL), Argonne, IL (United States)], Weingartz, Nicholas P. [Northwestern Univ., Evanston, IL (United States)], Kostopoulos, George T. [Univ. of Illinois, Chicago, IL (United States)], Chen, Lin X. [Argonne National Laboratory (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)] (ORCID:0000000284506687), Zapol, Peter [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000305709169), Agarwal, Neeraj [Univ. of Mumbai (India)] (ORCID:0000000328532730), Huerta, Eliu [Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of Chicago, IL (United States)] (ORCID:0000000296823604), Keceli, Murat [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000185889272), Chaudhuri, Santanu [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000243282947), Glusac, Ksenija D. [Univ. of Illinois, Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:000000022734057X). 2025-08-29. Photochemical CO 2 Reduction by a Postsynthetically Modified Zr-MOF. https://doi.org/10.1021/acs.inorgchem.5c02600

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