Photocatalytic Hydrogen Production from Water Using Heterogeneous Two-dimensional Rhodium Coordination Polymer [Rh2(p-BDC)2]n

Abstract

Heterogeneous dinuclear rhodium(II) coordination polymer, [Rh2(p-BDC)2]n (p-BDC = 1,4-benzenedicarboxylate), which formed self-assembly infinite two-dimentional slit sheets structure was performed as hydrogen production catalyst for photochemical reduction of water under visible light irradiation in the presence of a multicomponent system containing Ru(bpy)32+, MV2+, and EDTA–2Na.

Multifunctional Metal–Organic Frameworks for Photocatalysis

“…Under light irradiation for 4 h, the accumulated H 2 evolution was 41 μmol, affording a catalytic TON of 8.16 with respect to the Ru‐MOF and an apparent quantum yield of 4.82% at 450 nm was established. Following this work, Mori's group further investigated a series of substituted Ru‐MOFs and two Rh‐MOFs as co‐catalysts for the photocatalytic reduction of water to hydrogen in similar photochemical systems …”

Nitrogen and Hydrogen Gas Adsorption Properties of Microporous Ruthenium Coordination Polymers

“…4 ] n showed outstanding selectivity (＞99%) for oxidation of primary aliphatic alcohols with air without any additives at room temperature [8]. Recently, we have been also reported the photochemical hydrogen production from water using these microporous ruthenium and rhodium coordination polymers [9][10]. Therefore, our reported ruthenium or rhodium coordination polymers are utility materials for heterogeneous catalyst and the development of more effective catalyst is desirable.…”

“…However, in the viewpoint of catalysis, their metal ions could not expect high catalytic performance. Therefore, in our laboratory, various metal coordination polymers incorporated with dinuclear paddlewheel motif such as Ru 2 , Rh 2 ions were also reported [5][6][7][8][9][10][11]. These materials were focused on not only gas-adsorption but also heterogeneous catalyst.…”

Synthesis and characterizations of a paddlewheel-type dirhodium-based photoactive porous metal-organic framework

“…These functional properties are performed in the solvated or dispersed conditions in the solvent media. Recently, these types of complexes have been utilized as robust building blocks for porous metal-organic frameworks (MOFs) [12][13][14], extended coordination polymers (CPs) [15][16][17][18][19], and supramolecular complexes [20][21]. The merits of a paddlewheel-type dirhodium unit as an MOF building block are (1) the unit's axial site availability, i.e., the open metal site, as a potential site for functional solid-state activities, and (2) the structural robustness compared with other paddlewheel-type dimetal units (such as Cu 2 and Zn 2 ) because of the existence of the Rh\ \Rh single bond.…”

“…These MOFs were reported to exhibit highly efficient catalytic performance for both H-D exchange reactions [12] and olefin hydrogenation [13] even at a low-temperature (e.g., 200 K); moreover, they were reported to be useful as catalysts for photochemical H 2 evolution in the presence of a photosensitizer and an electron relay [14]. Interestingly, the catalytic performances of these MOFs were remarkably superior compared with related discrete dirhodium complexes such as [Rh 2 (O 2 CCH 3 ) 4 (H 2 O) 2 ], indicating that the immobilization of a dirhodium unit as a building block of a porous MOF is advantageous for the development of effective catalysts and functional materials.…”