Ryo Kuriki

Visible-Light-Driven CO2 Reduction with Carbon Nitride: Enhancing the Activity of Ruthenium Catalysts†

A heterogeneous photocatalyst system that consists of a ruthenium complex and carbon nitride (C3N4), which act as the catalytic and light-harvesting units, respectively, was developed for the reduction of CO2 into formic acid. Promoting the injection of electrons from C3N4 into the ruthenium unit as well as strengthening the electronic interactions between the two units enhanced its activity. The use of a suitable solvent further improved the performance, resulting in a turnover number of greater than 1000 and an apparent quantum yield of 5.7% at 400 nm. These are the best values that have been reported for heterogeneous photocatalysts for CO2 reduction under visible-light irradiation to date.

The effect of the pore-wall structure of carbon nitride on photocatalytic CO2 reduction under visible light

Carbon nitride (C3N4) polymers work as a vital component in a photocatalytic CO2 reduction assembly that operates under visible light when modified with a ruthenium complex, trans(Cl)-[Ru{4,4′-(CH2PO3H2)2-2,2′-bipyridine}(CO)2Cl2], (Ru) as a catalyst. Here we examined the effects of structural properties of carbon nitride on the photocatalytic performance for CO2 reduction into formic acid. Introduction of mesoporosity into the graphitic carbon nitride structure increased the specific surface area, leading to significant enhancement in activity. However, higher surface area (in other words, lower crystallinity) that originated from excessively introduced mesopores had a negative impact on activity, although it is a prerequisite to allow for adsorption of Ru on the carbon nitride surface. Thus, the activity was sensitive to specific surface area and crystallinity of carbon nitride, but is largely insensitive to the pore size and the volume.

Interfacial Manipulation by Rutile TiO2 Nanoparticles to Boost CO2 Reduction into CO on a Metal-Complex/Semiconductor Hybrid Photocatalyst

Metal-complex/semiconductor hybrids have attracted attention as photocatalysts for visible-light CO2 reduction, and electron transfer from the metal complex to the semiconductor is critically important to improve the performance. Here rutile TiO2 nanoparticles having 5-10 nm in size were employed as modifiers to improve interfacial charge transfer between semiconducting carbon nitride nanosheets (NS-C3N4) and a supramolecular Ru(II)-Re(I) binuclear complex (RuRe). The RuRe/TiO2/NS-C3N4 hybrid was capable of photocatalyzing CO2 reduction into CO with high selectivity under visible light (λ > 400 nm), outperforming an analogue without TiO2 by a factor of 4, in terms of both CO formation rate and turnover number (TON). The enhanced photocatalytic activity was attributed primarily to prolonged lifetime of free and/or shallowly trapped electrons generated in TiO2/NS-C3N4 under visible-light irradiation, as revealed by transient absorption spectroscopy. Experimental results also indicated that the TiO2 modifier served as a good adsorption site for RuRe, which resulted in the suppression of undesirable desorption of the complex, thereby contributing to the improved photocatalytic performance. This study presents the first successful example of interfacial manipulation in a metal-complex/semiconductor hybrid photocatalyst for improved visible-light CO2 reduction to produce CO.

A Stable, Narrow-Gap Oxyfluoride Photocatalyst for Visible-Light Hydrogen Evolution and Carbon Dioxide Reduction

Mixed anion compounds such as oxynitrides and oxychalcogenides are recognized as potential candidates of visible-light-driven photocatalysts since, as compared with oxygen 2p orbitals, p orbitals of less electronegative anion (e.g., N3-, S2-) can form a valence band that has more negative potential. In this regard, oxyfluorides appear unsuitable because of the higher electronegativity of fluorine. Here we show an exceptional case, an anion-ordered pyrochlore oxyfluoride Pb2Ti2O5.4F1.2 that has a small band gap (ca. 2.4 eV). With suitable modification of Pb2Ti2O5.4F1.2 by promoters such as platinum nanoparticles and a binuclear ruthenium(II) complex, Pb2Ti2O5.4F1.2 worked as a stable photocatalyst for visible-light-driven H2 evolution and CO2 reduction. Density functional theory calculations have revealed that the unprecedented visible-light-response of Pb2Ti2O5.4F1.2 arises from strong interaction between Pb-6s and O-2p orbitals, which is enabled by a short Pb-O bond in the pyrochlore lattice due to the fluorine substitution.

Undoped Layered Perovskite Oxynitride Li2LaTa2O6N for Photocatalytic CO2 Reduction with Visible Light

Abstract Oxynitrides are promising visible‐light‐responsive photocatalysts, but their structures are almost confined with three‐dimensional (3D) structures such as perovskites. A phase‐pure Li2LaTa2O6N with a layered perovskite structure was successfully prepared by thermal ammonolysis of a lithium‐rich oxide precursor. Li2LaTa2O6N exhibited high crystallinity and visible‐light absorption up to 500 nm. As opposed to well‐known 3D oxynitride perovskites, Li2LaTa2O6N supported by a binuclear RuII complex was capable of stably and selectively converting CO2 into formate under visible light (λ>400 nm). Transient absorption spectroscopy indicated that, as compared to 3D oxynitrides, Li2LaTa2O6N possesses a lower density of mid‐gap states that work as recombination centers of photogenerated electron/hole pairs, but a higher density of reactive electrons, which is responsible for the higher photocatalytic performance of this layered oxynitride.

Hybrid Z-scheme nanocomposites for photocatalysis

Abstract CO 2 reduction into energy-rich chemicals such as HCOOH and CO has attracted attention in recent years as a means of addressing the depletion of fossil fuels and the serious environmental problems accompanying their combustion and the concomitant CO 2 emissions. Metal complexes and semiconductors are known to be active photocatalysts for CO 2 reduction. By combining the good reduction ability of metal complexes for CO 2 reduction and the strong oxidation power of semiconductors, a new type of photocatalytic CO 2 reduction system could be constructed. In this chapter, photocatalytic and photoelectrochemical CO 2 reduction systems, which work according to the Z-scheme principle similar to natural photosynthesis in green plants, are presented.

Graphitic carbon nitride prepared from urea as a photocatalyst for visible-light carbon dioxide reduction with the aid of a mononuclear ruthenium(II) complex

Graphitic carbon nitride (g-C3N4) was synthesized by heating urea at different temperatures (773–923 K) in air, and was examined as a photocatalyst for CO2 reduction. With increasing synthesis temperature, the conversion of urea into g-C3N4 was facilitated, as confirmed by X-ray diffraction, FTIR spectroscopy and elemental analysis. The as-synthesized g-C3N4 samples, further modified with Ag nanoparticles, were capable of reducing CO2 into formate under visible light (λ > 400 nm) in the presence of triethanolamine as an electron donor, with the aid of a molecular Ru(II) cocatalyst (RuP). The CO2 reduction activity was improved by increasing the synthesis temperature of g-C3N4, with the maximum activity obtained at 873–923 K. This trend was also consistent with that observed in photocatalytic H2 evolution using Pt-loaded g-C3N4. The photocatalytic activities of RuP/g-C3N4 for CO2 reduction and H2 evolution were thus shown to be strongly associated with the generation of the crystallized g-C3N4 phase.

Metal-complex/semiconductor hybrids for carbon dioxide fixation

A hybrid photocatalyst consisting of a catalytic Ru complex and polymeric carbon nitride (band gap, 2.7 eV) was capable of reducing CO2 into HCOOH with ~80% selectivity under visible light (λ > 420 nm) in the presence of a suitable electron donor. Introduction of mesoporosity into the graphitic carbon nitride structure to increase the specific surface area was essential to enhancing the activity. However, higher surface area (in other words, lower crystallinity) that originated from excessively introduced mesopores had a negative impact on activity. Promoting electron injection from carbon nitride to the catalytic Ru unit as well as strengthening the electronic interactions between the two units improved the activity. Under the optimal condition, a turnover number (TON, with respect to the Ru complex used) greater than 1000 and an apparent quantum yield of 5.7% (at 400 nm) were obtained, which are the greatest among heterogeneous photocatalysts for visible-light CO2 reduction ever reported.