Precisely Tuning Band Gaps of Hexabenzocoronene-Based MOFs Toward Enhanced Photocatalysis

Hao Zhang; Cha Li; Feifan Lang; Mei Li; Haoyu Liu; Di-Chang Zhong; Jun-Sheng Qin; Zhengyi Di; Dan-Hong Wang; Le Zeng; Jiandong Pang; Xian-He Bu

doi:10.1002/anie.202418017

Precisely Tuning Band Gaps of Hexabenzocoronene-Based MOFs Toward Enhanced Photocatalysis

Angew Chem Int Ed Engl. 2024 Oct 23:e202418017. doi: 10.1002/anie.202418017. Online ahead of print.

Authors

Hao Zhang¹, Cha Li¹, Feifan Lang¹, Mei Li¹, Haoyu Liu¹, Di-Chang Zhong², Jun-Sheng Qin³, Zhengyi Di⁴, Dan-Hong Wang¹, Le Zeng¹, Jiandong Pang^{1

5}, Xian-He Bu^{1

6

5}

Affiliations

¹ School of Materials Science and Engineering, Smart Sensing Interdisciplinary Science Center, Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin, 300350, P. R. China.
² Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384, P. R. China.
³ International Center of Future Science, Jilin University, Changchun, 130012, P. R. China.
⁴ College of Chemistry, Tianjin Normal University, Tianjin, 300387, P. R. China.
⁵ Haihe Laboratory of Sustainable Chemical Transformations, Tianjin, 300192, P. R. China.
⁶ State Key Laboratory of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin, 300071, P. R. China.

PMID: 39444057
DOI: 10.1002/anie.202418017

Abstract

Precise adjusting the band gaps in metal-organic frameworks (MOFs) is crucial for improving their visible-light absorption capacity during photocatalysis, presenting both a formidable challenge and a charming opportunity. This present study employed a symmetry-reduction strategy to pre-design six novel 4-connected ligands with systematic substituents (-NO₂, -H, -^tBu, -OCH₃, -OH and -NH₂) and synthesized the corresponding pillared-layer Zr-MOFs (NKM-668) retaining the hexaphenylbenzene fragment. Subsequently, the NKM-668 MOFs were transformed into large-π-conjugated hexabenzocoronene-based MOFs (pNKM-668) via the Scholl reaction. These twelve MOFs exhibited broad and tunable band gaps over 1.41 eV (ranging from 3.25 eV to 1.84 eV), and the photocatalytic CO₂ conversion rate raised by 33.2-fold. This study not only enriches the type of hexaphenylbenzene-based MOFs, but also paves the way for nanographene-containing MOFs in the further application of photocatalysis.

Keywords: band gaps; hexabenzocoronene; metal-organic frameworks; photocatalysis.

Abstract

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