The reaction mechanism of photocatalytic CO2 reduction using rhenium(I) complexes has been investigated by means a detailed comparison the photocatalyses three complexes, fac-[Re(bpy)(CO)3L] (L = SCN- (1-NCS), Cl- (1-Cl), and CN- (1-CN)). corresponding one-electron-reduced species (OER) play two important roles in reaction: (a) capturing after loss monodentate ligand (L) (b) donation second electron to another OER without L. In case 1-NCS, both capabilities reaction, resulting more efficient...

A hybrid for the visible-light-driven photocatalytic reduction of CO2 using methanol as a reducing agent was developed by combining two different types photocatalysts: Ru(II) dinuclear complex (RuBLRu') used is adsorbed onto Ag-loaded TaON (Ag/TaON) oxidation. Isotope experiments clearly showed that this photocatalyst mainly produced HCOOH (TN = 41 9 h irradiation) from and HCHO methanol. Therefore, it converted light energy into chemical (ΔG° +83.0 kJ/mol). Photocatalytic reaction proceeds...

The decomposition of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water by UV−visible light irradiation, H2O2 with a tungstic heteropolyacid photocatalyst was examined to develop technique counteract stationary sources PFOA. Direct photolysis proceeded slowly produce CO2, F-, short-chain perfluorocarboxylic acids. Compared the direct photolysis, less effective PFOA decomposition. On other hand, led efficient production F- ions CO2. also suppressed accumulation acids...

Photocatalytic activity of graphitic carbon nitride (g-C3N4) was significantly improved by an alkaline hydrothermal treatment. The specific surface area g-C3N4 obtained heating melamine at 550 °C only 7.7 m2 g−1, which too small for it to be utilized as a catalyst air purification. By the treatment with NaOH solution 90–150 °C, increased up 65 and oxidation rate nitrogen oxide (NO) under visible light (380 < λ 480 nm) 8.6 times. XRD, ESR, elemental analysis electron microscopy showed that...

We study the electrochemical, spectroscopic, and photocatalytic properties of a series Ru(II)−Re(I) binuclear complexes linked by bridging ligands 1,3-bis(4'-methyl-[2,2']bipyridinyl-4-yl)propan-2-ol (bpyC3bpy) 4-methyl-4'-[1,10]phenanthroline-[5,6-d]imidazol-2-yl)bipyridine (mfibpy) tetranuclear complex in which three [Re(CO)3Cl] moieties are coordinated to central Ru using bpyC3bpy ligands. In complexes, 4,4'-dimethyl-2,2'-bipyridine (dmb) 4,4'-bis(trifluoromethyl)-2,2'-bipyridine...

Previously undescribed supramolecules constructed with various ratios of two kinds Ru(II) complexes-a photosensitizer and a catalyst-were synthesized. These complexes can photocatalyze the reduction CO(2) to formic acid high selectivity durability using wide range wavelengths visible light NADH model compounds as electron donors in mixed solution dimethylformamide-triethanolamine. Using higher ratio unit catalyst led yield acid. In particular, reported photocatalysts, trinuclear complex...

Reduction of CO2 using semiconductors as photocatalysts has recently attracted a great deal attention again. The effects organic adsorbates on the photocatalytic products are noteworthy. On untreated TiO2 (P-25) particles considerable number molecules such acetic acid were adsorbed. Although irradiation an aqueous suspension this resulted in formation significant amount CH4 major product, it was strongly suggested that its mainly proceeded via photo-Kolbe reaction acid. Using treated by...

An anatase type of TiO2 photocatalyst containing N atoms was synthesized by a new technique using complex Ti4+ with nitrogen-containing ligand as precursor. The TiO2-like prepared calcination Ti4+–bipyridine exhibited high photocatalytic activity for NOx removal under both ultraviolet and visible-light (λ < 645 nm) illumination. doping the atom into lattice, which is expected from UV-VIS spectroscopy, XRD, XPS, inferred an important factor visible light absorption wide range bipyridine acted...

The development of highly efficient, selective, and durable photocatalytic CO2 reduction systems that only use earth-abundant elements is key for both solving global warming tackling the shortage energy carbon resources. Here, we successfully developed photocatalysts using [Cu2(P2bph)2]2+ (CuPS) (P2bph = 4,7-diphenyl-2,9-di(diphenylphosphinotetramethylene)-1,10-phenanthroline) as a redox photosensitizer fac-Mn(X2bpy)(CO)3Br (Mn(4X)) (X2bpy 4,4'-X2-2,2'-bipyridine (X -H -OMe) or Mn(6mes)...

In an aqueous solution, photophysical, photochemical, and photocatalytic abilities of a Ru(II)-Re(I) binuclear complex (RuReCl), which Ru(II) photosensitizer Re(I) catalyst units were connected with bridging ligand, have been investigated in details. RuReCl could photocatalyze CO2 reduction using ascorbate as electron donor, even solution. The main product the reaction was formic acid solution; this is very different distribution from that dimethylformamide (DMF) triethanolamine (TEOA) mixed...

New Ru(II)–Re(I) supramolecular photocatalysts with a rhenium(I) biscarbonyl complex as catalyst unit were synthesized. They photocatalyzed CO2 reduction to CO using wide-range of visible light, and their photocatalytic abilities strongly affected by the phosphorus ligands on Re site. Especially, Ru–Re(FPh), two P(p-FPh)3 ligands, exhibited tremendous properties, i.e.TNCO = 207 ΦCO 0.15, and, in addition, this is one fastest-operating for CO, TFCO 281 h−1. We also clarified balance...

We synthesized for the first time a series of emissive ring-shaped Re(I) complexes (Re-rings) with various numbers units and lengths bridge ligands. The photophysical properties Re-rings could be varied widely through changes in size central cavity. A smaller cavity induced intramolecular π–π interactions between ligands consequently caused stronger emission longer lifetime excited state. can function as efficient durable photosensitizers. combination trinuclear Re-ring photosensitizer...

We discovered an extremely suitable sacrificial electron donor, 1,3-dimethyl-2-(o-hydroxyphenyl)-2,3-dihydro-1H-benzo[d]imidazole, for the selective photocatalytic reduction of CO2 to formic acid using a Ru(ii)-Ru(ii) supramolecular photocatalyst. The efficiency, durability, and rate photocatalysis are significantly increased (ΦHCOOH = 0.46, TONHCOOH 2766, TOFHCOOH 44.9 min-1) in comparison with those 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole or 1-benzyl-1,4-dihydronicotinamide.

The novel supramolecular complexes, which are composed of an [Os(5dmb)2(BL)](2+)-type complex (5dmb = 5,5'-dimethyl-2,2'-bipyridine; BL 1,2-bis(4'-methyl-[2,2'-bipyridin]-4-yl)ethane) as a photosensitizer and cis,trans-[Re(BL)(CO)2{P(p-X-C6H4)3}2](+)-type complexes (X F, Cl) catalyst, have been synthesized. They photocatalyzed selective reduction CO2 to CO under red-light irradiation (λ > 620 nm). photocatalytic abilities were affected by the phosphine ligands on Re unit, supramolecule with...

We report herein the mechanism of photochemical ligand substitution reactions a series fac-[Re(X(2)bpy)(CO)(3)(PR(3))](+) complexes (1) and properties their triplet ligand-field ((3)LF) excited states. The reason for photostability rhenium [Re(X(2)bpy)(CO)(3)(py)](+) (3) [Re(X(2)bpy)(CO)(3)Cl] (4) was also investigated. Irradiation an acetonitrile solution 1 selectively gave biscarbonyl cis,trans-[Re(X(2)bpy)(CO)(2)(PR(3))(CH(3)CN)](+) (2). Isotope experiments clearly showed that CO trans to...

Reduction of CO2 to CO was efficiently photocatalyzed by [Re(4,4'-X2bpy)(CO)3PR3]+ (X = H, Me; PR3 P(OEt)3, P(O-i-Pr)3) in quantum yields 0.16−0.20. Complexes with CF3 as X or trialkylphosphine have much lower photocatalytic ability. One-electron-reduced species the complexes, which were produced photoinduced electron-transfer reaction triethanolamine, reacted dark rate constants 3.5 × 10-4−1.9 10-2 M-1 s-1. The faster this process, higher yield formation. calculated amount formation, based...

Intramolecular interactions between ligands have been successfully applied as a novel tool for controlling various properties of series cis,trans-[Re(dmb)(CO)(2)(PR(3))(PR'(3))](+)-type complexes (dmb = 4,4'-dimethyl-2,2'-bipyridine), in the ground state and excited one-electron reduced form. For rhenium with two triarylphosphine ligands, P(p-XPh)(3), dmb ligand was sandwiched by four aryl rings having CH(aryl)-pi(pyridine)-pi(aryl) interactions. On other hand, one trialkylphosphite ligand,...

Abstract A photocatalytic system for CO 2 reduction exhibiting visible‐light harvesting was developed by preparing a hybrid consisting of supramolecular metal complex as photocatalyst and periodic mesoporous organosilica (PMO) light harvester. Ru II Re I binuclear (RuRe) with methylphosphonic acid anchor groups adsorbed on acridone or methylacridone embedded in the walls PMO mesochannels to yield structure. The organic absorbed visible light, excitation energy funneled units. accumulation...

Abstract The photochemistry of fac ‐[Re(bpy)(CO) 3 Cl] ( 1 a ; bpy=2,2′‐bipyridine) initiated by irradiation using &lt;330 nm light has been investigated. Isomerization proceeded in THF to give the corresponding mer‐ isomer b . However, presence small amount MeCN, main product was CO‐ligand‐substituted complex OC ‐6‐24)‐[Re(bpy)(CO) 2 Cl(MeCN)] c bpy=2,2′‐bipyridine). In two isomers, and its ‐6‐34) form ), were produced. Only thermally isomerized produce ‐6‐44) A detailed investigation led...