CO2-to-CO conversion with over 10% efficiency using earth abundant system in a single-compartment reactor with oxygen tolerant Mn complex catalyst.

The direct conversion of CO2 in flue gas to value-added chemicals is a potentially important cost-effective solar-driven CO2 reduction technology. The present work demonstrates the solar-powered conversion of CO2 to CO with greater than 10% efficiency using a Mn complex cathode and an Fe-Ni anode in a single-compartment reactor without an ion exchange membrane in conjunction with a Si solar cell. Reactors separated by ion exchange membranes are typically used to prevent any effects of oxygen generated by the counter electrode. However, the present Mn complex catalyst maintained its activity even in the presence of 15% O2. Operando surface-enhanced Raman spectroscopy established that the present Mn catalyst preferentially reacted with CO2 without adsorbing O2. This unique characteristic enabled solar-driven CO2 reduction using a single-compartment reactor. In contrast, catalytic metals such as Ag tend to lose activity in such systems as a consequence of reaction with oxygen produced at the anode.

Photocatalytic CO2 Reduction Using an Osmium Complex as a Panchromatic Self-Photosensitized Catalyst: Utilization of Blue, Green, and Red Light.

The photocatalytic reduction of carbon dioxide (CO2) represents an attractive approach for solar-energy storage and leads to the production of renewable fuels and valuable chemicals. Although some osmium (Os) photosensitizers absorb long wavelengths in the visible-light region, a self-photosensitized, mononuclear Os catalyst for red-light-driven CO2 reduction has not yet been exploited. Here, we discovered that the introduction of an Os metal to a PNNP-type tetradentate ligand resulted in the absorption of light with longer-wavelength (350-700 nm) and that can be applied to a panchromatic self-photosensitized catalyst for CO2 reduction to give mainly carbon monoxide (CO) with a total turnover number (TON) of 625 under photoirradiation (λ≥400 nm). CO2 photoreduction also proceeded under irradiation with blue (λ0=405 nm), green (λ0=525 nm), or red (λ0=630 nm) light to give CO with >90 % selectivity. The quantum efficiency using red light was determined to be 12 % for the generation of CO. A catalytic mechanism is proposed based on the detection of intermediates using various spectroscopic techniques, including transient absorption, electron paramagnetic resonance, and UV/Vis spectroscopy.

Enhanced performance of molecular electrocatalysts for CO2 reduction in a flow cell following K+ addition.

Electrocatalytic CO2 reduction is a key aspect of artificial photosynthesis systems designed to produce fuels. Although some molecular catalysts have good performance for CO2 reduction, these compounds also suffer from poor durability and energy efficiency. The present work demonstrates the improved CO2 reduction activity exhibited by molecular catalysts in a flow cell. These catalysts were composed of a cobalt-tetrapyridino-porphyrazine complex supported on carbon black together with potassium salt and were both stable and efficient. These systems were found to promote electrocatalytic CO2 reduction with a current density of 100 mA/cm2 and generated CO over at least 1 week with a selectivity of approximately 95%. The optimal catalyst gave a turnover number of 3,800,000 and an energy conversion efficiency of more than 62% even at 200 mA/cm2.

Highly selective CO2 electrolysis in aqueous media by a water-soluble cobalt dimethyl-bipyridine complex.

A water-soluble Co complex with dimethyl-bipyridine ligands reduced CO2 to CO electrochemically with almost 100% selectivity at -0.80 V vs. NHE in an aqueous medium (pH 6.8) without an organic solvent. The reaction overpotential was 270 mV. A possible CO formation mechanism was discussed based on experiments and calculations.

Importance of steric bulkiness of iridium photocatalysts with PNNP tetradentate ligands for CO2 reduction.

A series of Ir complexes has been developed as multifunctional photocatalysts for CO2 reduction to give HCO2H selectively. The catalytic activities and photophysical properties vary widely across the series, and the bulky group insertion resulted in the formation of HCO2H and CO with the catalyst turnover number of >10 400.

Solar-Driven CO2 Reduction Using a Semiconductor/Molecule Hybrid Photosystem: From Photocatalysts to a Monolithic Artificial Leaf.

The synthesis of organic chemicals from H2O and CO2 using solar energy is important for recycling CO2 through cyclical use of chemical ingredients produced from CO2 or molecular energy carriers based on CO2. Similar to photosynthesis in plants, the CO2 molecules are reduced by electrons and protons, which are extracted from H2O molecules, to produce O2. This reaction is uphill; therefore, the solar energy is stored as the chemical bonding energy in the organic molecules. This artificial photosynthetic technology mimicking green vegetation should be implemented as a self-standing system for on-site direct solar energy storage that supports CO2 recycling in a circular economy. Herein, we explain our interdisciplinary fusion methodology to develop hybrid photocatalysts and photoelectrodes for an artificial photosynthetic system for the CO2 reduction reaction (CO2RR) in aqueous solutions. The key factor for the system is the integration of uniquely different functions of molecular transition-metal complexes and solid semiconductors. A metal complex catalyst and a semiconductor appropriate for a CO2RR and visible-light absorption, respectively, are linked, and they function complementary way to catalyze CO2RR under visible-light irradiation as a particulate photocatalyst dispersion in solution. It has also been proven that Ru complexes with bipyridine ligands can catalyze a CO2RR as photocathodes when they are linked with various semiconductor surfaces, such as those of doped tantalum oxides, doped iron oxides, indium phosphides, copper-based sulfides, selenides, silicon, and others. These photocathodes can produce formate and carbon monoxide using electrons and protons extracted from water through potential-matched connections with photoanodes such as TiO2 or SrTiO3 for oxygen evolution reactions (OERs). Benefiting from the very low overpotential of an aqueous CO2RR at metal complexes approaching the theoretical lower limit, the semiconductor/molecule hybrid system demonstrates a single tablet-formed monolithic electrode called "artificial leaf." This single electrode device can generate formate (HCOO-) from H2O and CO2 in a water-filled single-compartment reactor without requiring a separation membrane under unassisted or bias-free conditions, either electrically or chemically. The reaction proceeds with a stoichiometric electron/hole ratio and stores solar energy with a solar-to-chemical energy conversion efficiency of 4.6%, which exceeds that of plants. In this Account, the key results that marked our milestones in technological progress of the semiconductor/molecule hybrid photosystem are concisely explained. These results include design, proof of the principle, and understanding of the phenomena by time-resolved spectroscopies, synchrotron radiation analyses, and DFT calculations. These results enable us to address challenges toward further scientific progress and the social implementation, including the use of earth-abundant elements and the scale-up of the solar-driven CO2RR system.

Study of Excited States and Electron Transfer of Semiconductor-Metal-Complex Hybrid Photocatalysts for CO2 Reduction by Using Picosecond Time-Resolved Spectroscopies.

A semiconductor-metal-complex hybrid photocatalyst was previously reported for CO2 reduction; this photocatalyst is composed of nitrogen-doped Ta2 O5 as a semiconductor photosensitizer and a Ru complex as a CO2 reduction catalyst, operating under visible light (>400 nm), with high selectivity for HCOOH formation of more than 75 %. The electron transfer from a photoactive semiconductor to the metal-complex catalyst is a key process for photocatalytic CO2 reduction with hybrid photocatalysts. Herein, the excited-state dynamics of several hybrid photocatalysts are described by using time-resolved emission and infrared absorption spectroscopies to understand the mechanism of electron transfer from a semiconductor to the metal-complex catalyst. The results show that electron transfer from the semiconductor to the metal-complex catalyst does not occur directly upon photoexcitation, but that the photoexcited electron transfers to a new excited state. On the basis of the present results and previous reports, it is suggested that the excited state is a charge-transfer state located between shallow defects of the semiconductor and the metal-complex catalyst.

Electrochemical CO2 reduction over nanoparticles derived from an oxidized Cu-Ni intermetallic alloy.

Oxide-derived Cu-Ni (3-32 at%-Ni) alloy nanoparticles with a size of 10 nm enhance selectivity for ethylene and ethanol formation over oxide-derived Cu nanoparticles by electrochemical CO2 reduction. X-ray absorption spectroscopy measurements suggest that Ni (generally recognized as an element to avoid) is in a mixed phase of oxidized and metallic states.

Photocatalytic CO2 Reduction Using a Robust Multifunctional Iridium Complex toward the Selective Formation of Formic Acid.

A highly efficient tetradentate PNNP-type Ir photocatalyst, Mes-IrPCY2, was developed for the reduction of carbon dioxide. The photocatalyst furnished formic acid (HCO2H) with 87% selectivity together with carbon monoxide to achieve a turnover number of 2560, which is the highest among CO2 reduction photocatalysts without an additional photosensitizer. Mes-IrPCY2 exhibited outstanding photocatalytic CO2 reduction activity in the presence of the sacrificial electron source 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) in CO2-saturated N,N-dimethylacetamide under irradiation with visible light. The quantum yield was determined to be 49% for the generation of HCO2H and CO. Electron paramagnetic resonance and UV-vis spectroscopy studies of Mes-IrPCY2 with a sacrificial electron donor revealed that the one-electron-reduced species is the key intermediate for the selective formation of HCO2H.

Photoelectrochemical water-splitting over a surface modified p-type Cr2O3 photocathode.

Cr2O3 is a p-type semiconductor with a negative conduction band minimum position suitable for photocathodic H2 generation. Therefore, Cr2O3 is a candidate photocathode material for photoelectrochemical (PEC) water-splitting. However, Cr2O3 has not yet been applied for the purpose of H2 generation because the efficiency and stability of the photocurrent generated by a Cr2O3 electrode are poor, due to high defect and vacancy concentrations. In the present work, the Cr2O3 surface was modified with n-type TiO2 after which Pt particles were deposited to catalyse H2 production. The TiO2 overlayer passivated the Cr2O3 surface states that otherwise cause deleterious interactions with the Pt particles. This layer also improved charge separation from the conduction band of Cr2O3 to the Pt co-catalyst, by forming a p-n junction. As a result of the TiO2 insertion, the cathodic photocurrent resulting from light absorption by Cr2O3 was enhanced and stabilized. This represents the first-ever use of Cr2O3 as a light-absorbing material in a multi-layered electrode to accomplish PEC water-splitting for H2 generation.

Molecular Catalysts Immobilized on Semiconductor Photosensitizers for Proton Reduction toward Visible-Light-Driven Overall Water Splitting.

Photocatalytic or photoelectrochemical hydrogen production by water splitting is one of the key reactions for the development of an energy supply that enables a clean energy system for a future sustainable society. Utilization of solar photon energy for the uphill water splitting reaction is a promising technology, and therefore many systems using semiconductor photocatalysts and semiconductor photoelectrodes for the reaction producing hydrogen and dioxygen in a 2:1 stoichiometric ratio have been reported. In these systems, molecular catalysts are also considered to be feasible; recently, systems based on molecular catalysts conjugated with semiconductor photosensitizers have been used for photoinduced hydrogen generation by proton reduction. Additionally, there are reports that the so-called Z-scheme (two-step photoexcitation) mechanism realizes the solar-driven uphill reaction by overall water splitting. Although the number of these reports is still small compared to those of all-inorganic systems, the advantages of molecular cocatalysts and its immobilization on a semiconductor are attractive. This Minireview provides a brief overview of approaches and recent research progress toward molecular catalysts immobilized on semiconductor photocatalysts and photoelectrodes for solar-driven hydrogen production with the stoichiometric uphill reaction of hydrogen and oxygen generation.

Solar-driven CO2 to CO reduction utilizing H2O as an electron donor by earth-abundant Mn-bipyridine complex and Ni-modified Fe-oxyhydroxide catalysts activated in a single-compartment reactor.

Photoelectrochemical CO2 to CO reduction was demonstrated with 3.4% solar-to-chemical conversion efficiency using polycrystalline silicon photovoltaic cells connected with earth-abundant catalysts: a manganese complex polymer for CO2 reduction and iron oxyhydroxide modified with a nickel compound for water oxidation. The system operated around neutral pH in a single-compartment reactor.

Band bending and dipole effect at interface of metal-nanoparticles and TiO2 directly observed by angular-resolved hard X-ray photoemission spectroscopy.

This paper describes the observation of band bending and band edge shifts at the interfaces between nanoscale metals and TiO2 film over a wide depth range by angular-resolved hard X-ray photoemission spectroscopy (HAXPES). The HAXPES results indicate strong electrostatic interactions between the TiO2 semiconductor and metal nanoparticles, while density functional theory (DFT) calculations suggest that these interactions are primarily associated with charge transfer leading to electric dipole moments at the interface in the ground state. The effects of these dipole moments are not limited to the surface but also occur deep in the bulk of the semiconductor, and are highly dependent on the coverage of the metal nanoparticles on the semiconductor species.

Visible-light-driven CO2 reduction on a hybrid photocatalyst consisting of a Ru(ii) binuclear complex and a Ag-loaded TaON in aqueous solutions.

A hybrid photocatalyst consisting of a Ru(ii) binuclear complex and a Ag-loaded TaON reduced CO2 by visible light even in aqueous solution. The distribution of the reduction products was strongly affected by the pH of the reaction solution. HCOOH was selectively produced in neutral conditions, whereas the formation of HCOOH competed with H2 evolution in acidic conditions. Detailed mechanistic studies revealed that the photocatalytic CO2 reduction proceeded via 'Z-schematic' electron transfer with step-by-step photoexcitation of TaON and the photosensitizer unit in the Ru(ii) binuclear complex. The maximum turnover number for HCOOH formation was 750 based on the Ru(ii) binuclear complex under visible-light irradiation, and the optimum external quantum efficiency of the HCOOH formation was 0.48% using 400 nm monochromic light with ethylenediaminetetraacetic acid disodium salt as a sacrificial reductant. Even in aqueous solution, the hybrid could also convert visible-light energy into chemical energy (ΔG0 = +83 kJ mol-1) by the reduction of CO2 to HCOOH with methanol oxidation.

Selective Formic Acid Production via CO2 Reduction with Visible Light Using a Hybrid of a Perovskite Tantalum Oxynitride and a Binuclear Ruthenium(II) Complex.

A hybrid material consisting of CaTaO2N (a perovskite oxynitride semiconductor having a band gap of 2.5 eV) and a binuclear Ru(II) complex photocatalytically produced HCOOH via CO2 reduction with high selectivity (>99%) under visible light (λ>400 nm). Results of photocatalytic reactions, spectroscopic measurements, and electron microscopy observations indicated that the reaction was driven according to a two-step photoexcitation of CaTaO2N and the Ru photosensitizer unit, where Ag nanoparticles loaded on CaTaO2N with optimal distribution mediated interfacial electron transfer due to reductive quenching.

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.

Structural improvement of CaFe2O4 by metal doping toward enhanced cathodic photocurrent.

Various metal-doped p-type CaFe2O4 photocathodes were prepared in an attempt to improve the low quantum efficiency for photoreaction. CuO and Au doping enhanced the photocurrent by expansion of the absorption wavelength region and plasmon resonance, respectively. X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) analysis showed that doping with these metals further disturbed the originally distorted crystal structure of CaFe2O4. In contrast, doping with Ag relaxed the distorted crystal structure around the Fe center toward symmetry. Ag doping resulted in improvement of the carrier mobility together with a red-shift of photoabsorption with Ag-doped CaFe2O4 having a 23-fold higher photocurrent than undoped CaFe2O4.

Hybridization between periodic mesoporous organosilica and a Ru(II) polypyridyl complex with phosphonic acid anchor groups.

A new method for the hybridization of a ruthenium(II) polypyridyl complex ([Ru(bpy)2((CH2PO3H2)2-bpy)](2+) (RuP2(2+): bpy =2,2'-bipyridine; (CH2PO3H2)2-bpy =2,2'-bipyridine-4,4'di(metylphosphonic acid)) with biphenylene-bearing periodic mesoporous organosilica (Bp-PMO made from 4,4'bis(triethoxysilyl)biphenyl [(C2H5O)3Si-(C6H4)2-Si(OC2H5)3]) was developed. Efficient and secure fixation of the ruthenium(II) complex with methylphosphonic acid groups (RuP2(2+)) in the mesopores of Bp-PMO occurred. This method introduced up to 660 µmol of RuP2(2+) in 1 g of Bp-PMO. Two modes of adsorption of RuP2(2+) in the mesopores of Bp-PMO were observed: one is caused by the chemical interaction between the methylphosphonic acid groups of RuP2(2+) and the silicate moieties of Bp-PMO and the other is attributed to aggregation of the RuP2(2+) complexes. In the case of the former mode, adsorbed RuP2(2+) (up to 80-100 µmol g(-1)) did not detach from Bp-PMO after washing with acetonitrile, dimethylformamide, or even water. Emission from the excited biphenylene (Bp) units was quantitatively quenched by the adsorbed RuP2(2+) molecules in cases where more than 60 µmol g(-1) of RuP2(2+) was adsorbed, and emission from RuP2(2+) was observed. Quantitative emission measurements indicated that emission from approximately 100 Bp units can be completely quenched by only one RuP2(2+) molecule in the mesopore, and photons absorbed by approximately 400 Bp units are potentially accumulated in one RuP2(2+) molecule.

A polymeric-semiconductor-metal-complex hybrid photocatalyst for visible-light CO(2) reduction.

A polymeric carbon nitride semiconductor is demonstrated to photocatalyse CO2 reduction to formic acid under visible light (λ > 400 nm) with a high turnover number (>200 for 20 hours) and selectivity (>80%), when coupled with a molecular ruthenium complex as a catalyst.

Artificial Z-scheme constructed with a supramolecular metal complex and semiconductor for the photocatalytic reduction of CO2.

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