In this study, we report the successful incorporation of the photoactive bis(4′-(4-carboxyphenyl)-terpyridine)ruthenium(II) (Ru(cptpy) 2 ) strut into a robust metal−organic framework (MOF), AUBM-4. The single crystal X-ray analysis revealed the formation of a new one-dimensional structure of Ru(cptpy) 2 complexes linked together by Zr atoms that are eight coordinated with O atoms. The chemically stable MOF structure was employed as an efficient photocatalyst for carbon dioxide conversion to formate under visible light irradiation. To the best of our knowledge, the obtained conversion rate is among the highest reported in the literature for similar systems. Our strategy of using the Ru(cptpy) 2 complex as a linker to construct the MOF catalyst appears to be very promising in artificial photosynthesis.
A new porous indium metal organic framework namely (AUBM-1) was successfully synthesized via a solvothermal reaction of pyromellitic acid and indium chloride. Single crystal X-ray analysis revealed the formation of a 3D framework with a pts topology. The resulting MOF structure showed high chemical stability at different pH values. Thus, the activated indium MOF was applied for As removal from water for the first time and showed a high arsenate uptake capacity of 103.1 mg g at neutral pH, which is higher than the commercial adsorbents (usually less than 100 mg g at neutral pH). Finally, the kinetics and thermodynamic studies revealed that the As adsorption was an endothermic process and followed a pseudo-second-order kinetic model.
Photocatalytic CO 2 reduction into formate (HCOO − ) has been widely studied with semiconductor and molecule-based systems, but it is rarely investigated with covalent organic frameworks (COFs). Herein, we report a novel donor−acceptor COF named Co-PI-COF composed of isoindigo and metallated porphyrin subunits that exhibits high catalytic efficiency (∼50 μmol formate g −1 h −1 ) at low-power visible-light irradiation and in the absence of rare metal cocatalysts. Density functional theory calculations and experimental diffusereflectance measurements are used to explain the origin of catalytic efficiency and the particularly low band gap (0.56 eV) in this material. The mechanism of photocatalysis is also studied experimentally and is found to involve electron transfer from the sacrificial agent to the excited Co-PI-COF. The observed high-efficiency conversion could be ascribed to the enhanced CO 2 adsorption on the coordinatively unsaturated cobalt centers, the narrow band gap, and the efficient transfer of the charge originating from the postsynthetic metallation. It is anticipated that this study will pave the way toward the design of new simple and efficient catalysts for photocatalytic CO 2 reduction into useful products.
A family of five host–guest assemblies comprising
different
metal ions inside a cuboid 12-palladium-oxo cage, [MO8Pd12L8]
n− (MPd
12
L
8
, M = ScIII, CoII, CuII, L
= AsO4
3–; M = CdII, HgII, L = PhAsO3
2–), was synthesized
and structurally characterized in the solid state by single-crystal
X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR),
and thermogravimetric analysis, and their solution and gas-phase stability
were validated by multinuclear NMR spectroscopy and electrospray-ionization
mass spectrometry (ESI-MS). The polyoxopalladates (POPs) ScPd
12
As
8
, CoPd
12
As
8
, and CuPd
12
As
8
represent the first three
examples of the MPd12As8 archetype. The unique
cubic ligand field of {MO8} allows for collecting the speciation
profiles of the POPs in solution using 45Sc and 113Cd NMR techniques. Detailed magnetic and electron paramagnetic resonance
(EPR) studies were performed on CuPd
12
As
8
. Catalytic studies
on MPd12As8 (M = CuII and CoII) supported on SBA-15 unveiled a guest metal-dependent structure–function
relationship, with CuPd
12
As
8
being the more efficient precatalyst
for the hydroconversion of o-xylene in a fixed-bed
reactor.
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