Ruthenium Complex-Incorporated Two-Dimensional Metal–Organic Frameworks for Cocatalyst-Free Photocatalytic Proton Reduction from Water

Abstract

Ultrathin two-dimensional (2D) nanosheets with efficient light-driven proton reduction activity were obtained through the exfoliation of novel metal–organic frameworks (MOF), which were synthesized by using a bis­(4′-carboxy-2,2′:6′,2″-terpyridine) ruthenium complex as a linker and 3d transition-metal (Mn, Co, Ni, and Zn) anions as nodes. The nanosheet of the Ni2+ node exhibits a photocatalytic hydrogen evolution rate of 923 ± 40 μmol g–1 h–1 at pH = 4.0, without the presence of any cocatalyst or cosensitizer. A combined experimental and theoretical study suggests a reductive quenched pathway for the photocatalytic hydrogen evolution by the nanosheet. The transition-metal nodes at the edge of the nanosheets are proposed as the active sites. Density functional theory (DFT) calculations attributed the different catalytic activities of the nanosheets to the discrepancy of H adsorption free energy at various transition-metal nodes.

Highly efficient fluorescent chemosensor for nitro antibiotic detection based on luminescent coordination polymers with 2,6-di(4-carboxyphenyl)pyrazine

“…As shown in Fig. 1 [42][43][44] The ligand DCPP serves as a μ 4 linker to connect four Zn II ions, where one carboxylate group adopts a chelating mode and the other acts as a bridge to join two Zn II ions. The nitrogen atom of the ligand also coordinates with a Zn II ion.…”

2D metal–organic framework-based materials for electrocatalytic, photocatalytic and thermocatalytic applications

“…2D MOFs and 2D MOF-supported photocatalysts have been investigated for hydrogen production in the last several years. 46,51,62,[167][168][169][170] For photocatalytic hydrogenation production, co-catalysts are usually introduced to inhibit electron/ hole recombination and provide sufficient active sites to cata-lyze surface reactions by reducing the activation energy. The noble metal Pt is the most common co-catalyst loaded onto the photocatalysts to achieve high performance.…”

“…174 Huo et al synthesized ultrathin 2D Ni-MOF nanosheets containing bis(4′carboxy-2,2′:6′,2″-terpyridine) ruthenium complex, [RuII (tpyCOOH) 2 ] 2+ , as a linker, and the obtained 2D Ni-MOF nanosheets exhibited a photocatalytic H 2 production rate of 923 ± 40 μmol g −1 h −1 at pH = 4.0 under visible light without any cocatalyst or co-sensitizer. 170 The authors attributed the excellent activity to the reductive quenching pathway involving electron transfer from the reduced Ru photosensitizer linkers to the catalytic Ni nodes. The high cost and extreme scarcity of precious metals (e.g., Pt) and pyridinium or the ruthenium complex significantly impede their industrial-scale applications in photocatalytic H 2 production.…”

Ruthenium‐based Conjugated Polymer and Metal‐organic Framework Nanocomposites for Glucose Sensing

“…PPG@Ru was synthesized based on the procedure reported by Cui et al [22] and Huoet al [23] Briefly, PPG (261 mg) and dichloride [Ru(bpy) 2 ] 2 + (72 mg) were dissolved in 250 mL distilled water. The temperatureof mixture was maintained at95-100 °Cunder argon gas for 24 h, andthen cooled to20-30 °C for a further 24 h. The resulting product was dried undervacuum at 60 °C for 18 h.…”