Selective CO_(2) reduction into formate using Ln-Ta oxynitrides combined with a binuclear Ru(Ⅱ)complex under visible light

Hybrid materials constructed from a visible-light-absorbing semiconductor and a functional metal complex have attracted attention as efficient photocatalysts for CO_(2) reduction with high selectivity to a desired product.In this work,defect fluorite-type Ln-Ta oxynitrides LnTaO_(x)N_(y)(Ln=Nd,Sm,Gd,Tb,Dy and Ho)were examined as the semiconductor component in a hybrid photocatalyst system combined with known Ag nanoparticle promoter and binuclear ruthenium(Ⅱ)complex(RuRu’).Among the LnTaO_(x)N_(y) examined,TbTaO_(x)N_(y) gave the highest performance for CO_(2) reduction under visible light(k>400 nm),with a Ru Ru0-based turnover number of 18 and high selectivity to formate(>99%).Physicochemical analyses indicated that high crystallinity and more negative conduction band potential of Ln Ta O_(x)N_(y)with the absence of Ln-4 f states in the band gap structure contributed to higher activity of the hybrid photocatalyst.

Molecule/Semiconductor Hybrid Materials for Visible-Light CO_(2) Reduction:Design Principles and Interfacial Engineering

CONSPECTUS:Because of increasing concerns over the depletion of energy sources and the concomitant increase in CO_(2)emissions,much attention has been devoted to carbon capture and utilization technologies.Among the various methods and schemes proposed,visible-light-driven CO_(2)reduction in combination with water oxidation,one of the representative models of artificial photosynthesis,is an attractive solution because it enables abundant water and inexhaustible solar energy to be used to produce value-added chemicals.Molecular metal complexes and semiconductors are promising candidates for photocatalysts that can reduce CO_(2)to CO,formate,formaldehyde,or other hydrocarbons.Although both molecular metal complexes and semiconductors have strengths and weaknesses,their weaknesses(low oxidation ability and low selectivity for reduction reactions)can be overcome via the construction of a suitable molecule/semiconductor hybrid material.However,facilitating electron transfer at the molecule/semiconductor junction while suppressing unfavorable back electron transfer events is challenging.Consequently,the number of molecule/semiconductor hybrid systems that show a reasonable level of visible-light photocatalytic activity is limited,despite the development of a large number of visible-light-driven semiconductors and molecular photocatalysts(or catalysts).In this Account,we describe our approaches to developing hybrid photocatalysts and photoelectrodes for CO_(2)reduction.We have been developing both molecular(photo)catalysts and semiconductor photocatalysts individually,the latter of which are also designed for visible-light water splitting.For example,supramolecular photocatalysts that possess both photosensitizer and catalyst units in a single molecule can reduce CO_(2)to formate or CO in a homogeneous system,with high selectivity toward the desired product and high quantum yields of several tens of percent.However,nonoxide semiconductors such as C/N-based polymers and mixed-anion compounds exhibit a strong photooxidation ability under visible light.Carefully designed molecule/semiconductor hybrid materials achieve CO_(2)reduction under visible light with high product selectivity and stability even in an aqueous environment,where the concentration of CO_(2)is low but that of protons is high.Visible-light CO_(2)reduction combined with H2O oxidation is possible via the construction of a photoelectrochemical cell that comprises a molecular photocathode and an n-type semiconductor photoanode.Although our photosystems can be regarded as model systems for artificial photosynthesis,their light-energy conversion efficiencies are still unsatisfactory.To improve the efficiency,materials design,including interfacial engineering at the molecule/semiconductor junction,is important and is the general theme of the results highlighted in this Account.