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As the first example of a photocatalytic system for splitting water without additional cocatalysts and photosensitizers, the comparatively cost-effective Cu I -based MOF, Cu-I-bpy (bpy=4,4'-bipyridine) exhibited highly efficient photocatalytic hydrogen production (7.09 mmol g h ). Density functional theory (DFT) calculations established the electronic structures of Cu-I-bpy with a narrow band gap of 2.05 eV, indicating its semiconductive behavior, which is consistent with the experimental value of 2.00 eV. The proposed mechanism demonstrates that Cu I clusters of Cu-I-bpy serve as photoelectron generators to accelerate the copper(I) hydride interaction, providing redox reaction sites for hydrogen evolution. The highly stable cocatalyst-free and self-sensitized Cu-I-bpy provides new insights into the future design of cost-effective d -based MOFs for highly efficient and long-term solar fuels production.

Selective adsorption and separation of CO2 are of great importance for different target applications. Metal-organic frameworks (MOFs) represent a promising class of porous materials for this purpose. Here we present a unique MOF material, [Cu(tba)2]n (tba = 4-(1H-1,2,4-triazol-1-yl)benzoate), which shows high CO2 adsorption selectivity over CH4/H2/O2/Ar/N2 gases (with IAST selectivity of 41-68 at 273 K and 33-51 at 293 K). By using a critical point dryer, the CO2 molecules can be well sealed in the 1D channels of [Cu(tba)2]n to allow a single-crystal X-ray analysis, which reveals the presence of not only C(δ+)-H···O(δ-) bonds between the host framework and CO2 but also quadrupole-quadrupole (CO2(δ-)···(δ+)CO2) interactions between the CO2 molecules. Furthermore, [Cu(tba)2]n will suffer divergent kinetic and thermodynamic hydration processes to form its isostructural hydrate {[Cu(tba)2](H2O)}n and a mononuclear complex [Cu(tba)2(H2O)4] via single-crystal to single-crystal transformations.

The template-directed synthesis of a novel luminescent Tb-MOF material which could serve as a multi-responsive probe for sensing Fe3+ and Al3+ ions in water, as well as p-xylene and nitrobenzene in the vapor state is presented here.