Metal-complex chromophores for solar hydrogen generation

Abstract

Solar H generation from water has been intensively investigated as a clean method to convert solar energy into hydrogen fuel. During the past few decades, many studies have demonstrated that metal complexes can act as efficient photoactive materials for photocatalytic H production. Here, we review the recent progress in the application of metal-complex chromophores to solar-to-H conversion, including metal-complex photosensitizers and supramolecular photocatalysts. A brief overview of the fundamental principles of photocatalytic H production is given. Then, different metal-complex photosensitizers and supramolecular photocatalysts are introduced in detail, and the most important factors that strictly determine their photocatalytic performance are also discussed. Finally, we illustrate some challenges and opportunities for future research in this promising area.

Experimental and Theoretical Investigation of the Light‐Driven Hydrogen Evolution by Polyoxometalate–Photosensitizer Dyads

“…Lower maximum turnover numbers are observed for Ir‐POM Co ( TON =34) and Ir‐POM Fe ( TON =20). In comparison, other non‐POM based covalent dyads (many of them noble‐metal‐based) feature typical TONs in the ten to several hundred region . Notably, electrochemical, UV/Vis, and emission spectroscopic stability studies show that no cluster degradation (e.g., by cleavage of the imine bond) is observed during catalysis, so that a similar chemical stability can be suggested for the three Ir‐POM dyads (see the Supporting Information).…”

Engineering oxygen vacancy on rutile TiO2 for efficient electron-hole separation and high solar-driven photocatalytic hydrogen evolution

“…Hence, photocatalytic hydrogen production attracts much more attention recently [2][3][4]. Since Fujishima and Honda [5][6][7] discovered hydrogen production from water splitting on TiO 2 for the first time, it is considered as the most promising photocatalyst candidate due to nontoxicity, high stability and low-cost [8][9][10].…”

Influence of Hetero‐Biaryl Ligands on the Photo‐Electrochemical Properties of [ReINCS(N∩N)(CO)3]‐Type Photosensitizers

“…The introduction of pydz (12)(13)(14)(15) and bdz (16)(17)(18)(19) ligands with one or two additional nitrogen atoms respectively reduce the σdonor but increase π-acceptor ability of the diimine systems. [46] These modulations are reflected in the electrochemical and spectroscopic data presented here.…”

“…Metal complexes featuring diimine (N ∩ N) ligands have been studied in great detail for a long time [1] and have found broad applications in various fields such as photocatalysis (in organic synthesis, [2] water oxidation [3][4][5][6] and reduction catalysts, [6][7][8][9][10][11][12] CO 2 reduction catalysts [13][14][15][16][17][18][19] ) and many more. It allows the fine-tuning of absorption and emission properties by subtle structural variations.…”

“…The additional nitrogen atoms in pydz (12)(13)(14)(15) and bdz (16)(17)(18)(19) ligands lead to reduced σ-donor strength as well as a Scheme 1. The additional nitrogen atoms in pydz (12)(13)(14)(15) and bdz (16)(17)(18)(19) ligands lead to reduced σ-donor strength as well as a Scheme 1.…”