Controlled electron transfer by molecular wires embedded in ultrathin insulating membranes for driving redox catalysis.

Organic bilayers or amorphous silica films of a few nanometer thickness featuring embedded molecular wires offer opportunities for chemically separating while at the same time electronically connecting photo- or electrocatalytic components. Such ultrathin membranes enable the integration of components for which direct coupling is not sufficiently efficient or stable. Photoelectrocatalytic systems for the generation or utilization of renewable energy are among the most prominent ones for which ultrathin separation layers open up new approaches for component integration for improving efficiency. Recent advances in the assembly and spectroscopic, microscopic, and photoelectrochemical characterization have enabled the systematic optimization of the structure, energetics, and density of embedded molecular wires for maximum charge transfer efficiency. The progress enables interfacial designs for the nanoscale integration of the incompatible oxidation and reduction catalysis environments of artificial photosystems and of microbial (or biomolecular)-abiotic systems for renewable energy.

Precise Colloidal Plasmonic Photocatalysts Constructed by Multistep Photodepositions.

Natural photosynthesis relies on a sophisticated charge transfer pathway among multiple components with precise spatial, energetic, and temporal organizations in the aqueous environment. It continues to inspire and challenge the design and fabrication of artificial multicomponent colloidal nanostructures for solar-to-fuel conversion. Herein, we introduce a plasmonic photocatalyst synthesized with colloidal methods with five integrated components including cocatalysts installed in orthogonal locations. The precise deposition of individual inorganic components on an Au/TiO2 nanodumbell nanostructure is enabled by photoreduction and photo-oxidation, which selectively occurs at the TiO2 tip sites and Au lateral sites, respectively. Under visible-light irradiation, the photocatalyst exhibited activity of oxygen evolution from water without scavengers. We demonstrate that each component is essential for improving the photocatalytic performance. In addition, mechanistic studies suggest that the photocatalytic reaction requires combining the hot charge carriers derived from exciting both the d-sp interband transition and the localized surface plasmon resonance of Au.

Spectroscopic Characterization of µ-η1:η1-Peroxo Ligands Formed by Reaction of Dioxygen with Electron-Rich Iridium Clusters.

Although oxygen is a common ligand in supported metal catalysts, its coordination has been challenging to elucidate. We now characterize a diiridium complex that has been previously shown by X-ray diffraction crystallography to incorporate a µ-η1:η1-peroxo ligand. We observe markedly enhanced intensity at 788 cm-1 in the Raman spectrum of this complex, which is a consequence of bonding of the peroxo ligand but does not shift upon 18O labeling. Electronic structure calculations at the density functional theory level suggest that this increase in Raman intensity results from bands associated with rocking of CH2 substituents directly attached to P(Ph)2 groups coupling with the O-O band. These results provide part of the foundation for understanding oxygen ligands on a silica-supported tetrairidium carbonyl cluster stabilized with bulky electron-donating phosphine ligands [p-tert-butyl-calix[4]arene(OPr)3(OCH2PPh2) (Ph = phenyl; Pr = propyl)]. Reaction of the cluster with O2 also led to the growing in of a Raman band at 788 cm-1, similar to that in the diiridium complex and also assigned to the bonding of a bridging peroxo ligand. Infrared spectra recorded as the supported cluster reacted in sequential exposures to (i) H2, (ii) O2, (iii) H2, and (iv) CO indicate that two bridging peroxo ligands were bonded irreversibly per tetrairidium cluster, replacing bridging carbonyl ligands without altering either the cluster frame or the phosphine ligands. X-ray absorption near edge and infrared spectra include isosbestic points signifying a stoichiometrically simple reaction of the cluster with O2, and mass spectra of the effluent gas show that CO2 formed by oxidation of one terminal CO ligand per cluster as H2 (and not H2O) formed, evidence that hydride ligands had been present on the cluster following treatment (i). The understanding of how O2 reacts with the metal polyhedron provides a foundation for understanding of how oxidation catalysis may proceed on the surfaces of noble metals.

Ultrathin oxide layers for nanoscale integration of molecular light absorbers, catalysts, and complete artificial photosystems.

Artificial photosynthesis is an attractive approach for the generation of renewable fuels because such systems will be suitable for deployment on highly abundant, non-arable land. Recently emerged methods of nanoscience to create conformal, ultrathin oxide layers enable the hierarchical integration of light absorbers, catalysts, and membranes into systems with far simpler synthetic approaches than available till now. This holds in particular for the coupling of molecular light absorbers and catalysts for sunlight to fuel conversion, providing photoelectrodes with greatly improved stability. Moreover, the use of ultrathin inert oxides as proton conducting, molecule impermeable membranes has opened up the integration of reduction and oxidation half reactions into complete photosynthetic systems on the shortest possible length scale-the nanometer scale. This capability affords minimization of energy-degrading resistance losses caused by ion transport over macroscale distances while separating the incompatible water oxidation and carbon dioxide reduction catalysis environments on the nanoscale. Understanding of charge transport between molecular components embedded in the oxide layers is critical for guiding synthetic design improvements of the light absorber-catalyst units to optimize performance and integrate them into complete artificial photosystems. Recent results and insights from transient optical, vibrational, and photoelectrochemical studies are presented, and future challenges and opportunities for engaging dynamic spectroscopies to accelerate the development of nanoscale integrated artificial photosystems are discussed.

Carbon Dioxide Dimer Radical Anion as Surface Intermediate of Photoinduced CO2 Reduction at Aqueous Cu and CdSe Nanoparticle Catalysts by Rapid-Scan FT-IR Spectroscopy.

Monitoring of visible light sensitized reduction of CO2 at Cu nanoparticles in aqueous solution by rapid-scan ATR FT-IR spectroscopy on the time scale of seconds allowed structural identification of a one-electron intermediate and demonstrated its kinetic relevancy for the first time. Isotopic labeling (12C: 1632, 1358, 1346 cm-1; 13C: 1588, 1326, 1316 cm-1) revealed a species of carbon dioxide dimer radical anion structure, most likely bound to the catalyst surface through carbon. Intermediacy of Cu-C(═O)OCO2- surface species is in agreement with a recently proposed mechanism for electrocatalytic CO2 reduction at Cu metal nanoparticles based on Tafel slope analysis. Spontaneous decrease of the intermediate after termination of the photosensitization pulse (Sn porphyrin excited at 405 nm) was accompanied by the growth of HCO3-. CO was produced as well, but sensitive detection required photolysis for tens of minutes. A direct kinetic link between a C2O4- surface intermediate and the CO product was also demonstrated for photocatalyzed CO2 reduction at aqueous CdSe nanoparticles, where first order growth of a Cd-C(═O)OCO2- species was accompanied by rise of CO (monitored by a fast Ni complex trap) and HCO3- showing a distinct induction period. The detection of the one-electron surface intermediate and confirmation of its catalytic relevancy was enabled by the delivery of electrons one-by-one by the photosensitization method. The observation of carbon dioxide dimer radical anion points to approaches for rate enhancements of heterogeneous CO2 reduction by creating catalytic environments that favor formation of this intermediate.

Water Oxidation Mechanisms of Metal Oxide Catalysts by Vibrational Spectroscopy of Transient Intermediates.

Water oxidation is an essential reaction of an artificial photosystem for solar fuel generation because it provides electrons needed to reduce carbon dioxide or protons to a fuel. Earth-abundant metal oxides are among the most attractive catalytic materials for this reaction because of their robustness and scalability, but their efficiency poses a challenge. Knowledge of catalytic surface intermediates gained by vibrational spectroscopy under reaction conditions plays a key role in uncovering kinetic bottlenecks and provides a basis for catalyst design improvements. Recent dynamic infrared and Raman studies reveal the molecular identity of transient surface intermediates of water oxidation on metal oxides. Combined with ultrafast infrared observations of how charges are delivered to active sites of the metal oxide catalyst and drive the multielectron reaction, spectroscopic advances are poised to play a key role in accelerating progress toward improved catalysts for artificial photosynthesis.

Ultrafast Charge Transfer between Light Absorber and Co3O4 Water Oxidation Catalyst across Molecular Wires Embedded in Silica Membrane.

The mechanism of visible light-induced hole transfer from a molecular light absorber, in the form of a free-base porphyrin, coupled to a Co3O4 nanoparticle catalyst for water oxidation by a molecular wire (p-oligo(phenylenevinylene) featuring three aryl units) is investigated by transient absorption spectroscopy. The wires are covalently anchored on the Co3O4 surface and embedded in a dense, yet ultrathin (2 nm), silica layer that separates light absorber and catalyst. The porphyrin is electrostatically adsorbed on the silica surface, and aqueous colloidal solutions of the core-shell particles are used for transient optical measurements. Pulsed optical excitation of the porphyrin results in rapid injection of the photogenerated hole onto the molecular wire and concurrent formation of reduced light absorber in less than 1 picosecond (ps). Ultrafast charge separation was monitored by transient absorption of the wire radical cation, which is given by bands in the 500 to 600 nm region and at 1130 nm, while formation of reduced porphyrin was characterized by absorption at 700 nm. Forward transfer of the hole to Co3O4 catalyst proceeds in 255 ± 23 ps. Ultrafast transfer of positive charge from the molecular assembly to a metal oxide nanoparticle catalyst for water oxidation is unprecedented. Holes on Co3O4 recombined with electrons of the reduced sensitizer with biphasic kinetics on a much longer time scale of ten to several hundred nanoseconds. The unusually efficient hole transfer coupling of a molecular light absorber with an Earth-abundant metal oxide catalyst by silica-embedded p-oligo(phenylenevinylene) offers an approach for integrated artificial photosystems featuring product separation on the nanoscale.

Hierarchical Inorganic Assemblies for Artificial Photosynthesis.

Artificial photosynthesis is an attractive approach for renewable fuel generation because it offers the prospect of a technology suitable for deployment on highly abundant, non-arable land. Recent leaps forward in the development of efficient and durable light absorbers and catalysts for oxygen evolution and the growing attention to catalysts for carbon dioxide activation brings into focus the tasks of hierarchically integrating the components into assemblies for closing of the photosynthetic cycle. A particular challenge is the efficient coupling of the multi-electron processes of CO2 reduction and H2O oxidation. Among the most important requirements for a complete integrated system are catalytic rates that match the solar flux, efficient charge transport between the various components, and scalability of the photosynthetic assembly on the unprecedented scale of terawatts in order to have impact on fuel consumption. To address these challenges, we have developed a heterogeneous inorganic materials approach with molecularly precise control of light absorption and charge transport pathways. Oxo-bridged heterobinuclear units with metal-to-metal charge-transfer transitions absorbing deep in the visible act as single photon, single charge transfer pumps for driving multi-electron catalysts. A photodeposition method has been introduced for the spatially directed assembly of nanoparticle catalysts for selective coupling to the donor or acceptor metal of the light absorber. For CO2 reduction, a Cu oxide cluster is coupled to the Zr center of a ZrOCo light absorber, while coupling of an Ir nanoparticle catalyst for water oxidation to the Co donor affords closing of the photosynthetic cycle of CO2 conversion by H2O to CO and O2. Optical, vibrational, and X-ray spectroscopy provide detailed structural knowledge of the polynuclear assemblies. Time resolved visible and rapid-scan FT-IR studies reveal charge transfer mechanisms and transient surface intermediates under photocatalytic conditions for guiding performance improvements. Separation of the water oxidation and carbon dioxide reduction half reactions by a membrane is essential for efficient photoreduction of CO2 by H2O to liquid fuel products. A concept of a macroscale artificial photosystem consisting of arrays of Co oxide-silica core-shell nanotubes is introduced in which each tube operates as a complete, independent photosynthetic unit with built-in membrane separation. The ultrathin amorphous silica shell with embedded molecular wires functions as a proton conducting, molecule impermeable membrane. Photoelectrochemical and transient optical measurements confirm tight control of charge transport through the membrane by the orbital energetics of the wire molecules. Hierarchical arrangement of the components is accomplished by a combination of photodeposition, controlled anchoring, and atomic layer deposition methods.

Coupling carbon dioxide reduction with water oxidation in nanoscale photocatalytic assemblies.

The reduction of carbon dioxide by water with sunlight in an artificial system offers an opportunity for utilizing non-arable land for generating renewable transportation fuels to replace fossil resources. Because of the very large scale required for the impact on fuel consumption, the scalability of artificial photosystems is of key importance. Closing the photosynthetic cycle of carbon dioxide reduction and water oxidation on the nanoscale addresses major barriers for scalability as well as high efficiency, such as resistance losses inherent to ion transport over macroscale distances, loss of charge and other efficiency degrading processes, or excessive need for the balance of system components, to mention a few. For the conversion of carbon dioxide to six-electron or even more highly reduced liquid fuel products, introduction of a proton conducting, gas impermeable separation membrane is critical. This article reviews recent progress in the development of light absorber-catalyst assemblies for the reduction and oxidation half reactions with focus on well defined polynuclear structures, and on novel approaches for optimizing electron transfer among the molecular or nanoparticulate components. Studies by time-resolved optical and infrared spectroscopy for the understanding of charge transfer processes between the chromophore and the catalyst, and of the mechanism of water oxidation at metal oxide nanocatalysts through direct observation of surface reaction intermediates are discussed. All-inorganic polynuclear units for reducing carbon dioxide by water at the nanoscale are introduced, and progress towards core-shell nanotube assemblies for completing the photosynthetic cycle under membrane separation is described.

Direct Observation by Rapid-Scan FT-IR Spectroscopy of Two-Electron-Reduced Intermediate of Tetraaza Catalyst [Co(II)N4H(MeCN)](2+) Converting CO2 to CO.

In the search for the two-electron-reduced intermediate of the tetraaza catalyst [Co(II)N4H(MeCN)](2+) (N4H = 2,12-dimethyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),2,11,13,15-pentaene) for CO2 reduction and elementary steps that result in the formation of CO product, rapid-scan FT-IR spectroscopy of the visible-light-sensitized catalysis, using Ir(ppy)3 in wet acetonitrile (CD3CN) solution, led to the observation of two sequential intermediates. The initially formed one-electron-reduced [Co(I)N4H](+)-CO2 adduct was converted by the second electron to a transient [Co(I)N4H](+)-CO2(-) complex that spontaneously converted CO2 to CO in a rate-limiting step on the second time scale in the dark under regeneration of the catalyst (room temperature). The macrocycle IR spectra of the [Co(I)N4H](+)-CO2(-) complex and the preceding one-electron [Co(I)N4H](+)-CO2 intermediate show close similarity but distinct differences in the carboxylate modes, indicating that the second electron resides mainly on the CO2 ligand. Vibrational assignments are corroborated by (13)C isotopic labeling. The structure and stability of the two-electron-reduced intermediate derived from the time-resolved IR study are in good agreement with recent predictions by DFT electronic structure calculations. This is the first observation of an intermediate of a molecular catalyst for CO2 reduction during the bond-breaking step producing CO. The reaction pathway for the Co tetraaza catalyst uncovered here suggests that the competition between CO2 reduction and proton reduction of a macrocyclic multi-electron catalyst is steered toward CO2 activation if the second electron is directly captured by an adduct of CO2 and the one-electron-reduced catalyst intermediate.

Light induced carbon dioxide reduction by water at binuclear ZrOCo(II) unit coupled to Ir oxide nanocluster catalyst.

An all-inorganic polynuclear unit consisting of an oxo-bridged binuclear ZrOCo(II) group coupled to an iridium oxide nanocluster (IrO(x)) was assembled on an SBA-15 silica mesopore surface. A photodeposition method was developed that affords coupling of the IrO(x) water oxidation catalyst with the Co donor center. The approach consists of excitation of the ZrOCo(II) metal-to-metal charge-transfer (MMCT) chromophore with visible light in the presence of [Ir(acac)3] (acac: acetylacetonate) precursor followed by calcination under mild conditions, with each step monitored by optical and infrared spectroscopy. Illumination of the MMCT chromophore of the resulting ZrOCo(II)-IrO(x) units in the SBA-15 pores loaded with a mixture of (13)CO2 and H2O vapor resulted in the formation of (13)CO and O2 monitored by FT-IR and mass spectroscopy, respectively. Use of (18)O labeled water resulted in the formation of (18)O2 product. This is the first example of a closed photosynthetic cycle of carbon dioxide reduction by water using an all-inorganic polynuclear cluster featuring a molecularly defined light absorber. The observed activity implies successful competition of electron transfer between the IrO(x) catalyst cluster and the transient oxidized Co donor center with back electron transfer of the ZrOCo light absorber, and is further aided by the instant desorption of the CO and O2 product from the silica pores.

Dual visible light photoredox and gold-catalyzed arylative ring expansion.

A combination of visible light photocatalysis and gold catalysis is applied to a ring expansion-oxidative arylation reaction. The reaction provides an entry into functionalized cyclic ketones from the coupling reaction of alkenyl and allenyl cycloalkanols with aryl diazonium salts. A mechanism involving generation of an electrophilic gold(III)-aryl intermediate is proposed on the basis of mechanistic studies, including time-resolved FT-IR spectroscopy.

Efficient and sustained photoelectrochemical water oxidation by cobalt oxide/silicon photoanodes with nanotextured interfaces.

Plasma-enhanced atomic layer deposition of cobalt oxide onto nanotextured p(+)n-Si devices enables efficient photoelectrochemical water oxidation and effective protection of Si from corrosion at high pH (pH 13.6). A photocurrent density of 17 mA/cm(2) at 1.23 V vs RHE, saturation current density of 30 mA/cm(2), and photovoltage greater than 600 mV were achieved under simulated solar illumination. Sustained photoelectrochemical water oxidation was observed with no detectable degradation after 24 h. Enhanced performance of the nanotextured structure, compared to planar Si, is attributed to a reduced silicon oxide thickness that provides more intimate interfacial contact between the light absorber and catalyst. This work highlights a general approach to improve the performance and stability of Si photoelectrodes by engineering the catalyst/semiconductor interface.

Inorganic core-shell assemblies for closing the artificial photosynthetic cycle.

Co oxide (Co(3)O(4)) nanotubes are shown to act as an efficient water oxidation catalyst when driven with a visible light sensitizer (pH 7). The nanotubes form the core of a Co(3)O(4)-SiO(2) core-shell nanotube design for separating the carbon dioxide photoreduction from the oxygen evolution reaction. Amorphous dense phase silica of a few nanometers depth is shown to conduct protons while blocking molecular oxygen. Organic molecular wires embedded in the silica shell provide controlled charge transport between the light absorber on one side and the Co(3)O(4) catalyst on the other side. Hence, the silica shell is suitable as a membrane of an assembly for closing the photosynthetic cycle on the nanometer scale under product separation.

Visible light-induced hole injection into rectifying molecular wires anchored on Co3O4 and SiO2 nanoparticles.

Tight control of charge transport from a visible light sensitizer to a metal oxide nanoparticle catalyst for water oxidation is a critical requirement for developing efficient artificial photosynthetic systems. By utilizing covalently anchored molecular wires for hole transport from sensitizer to the oxide surface, the challenge of high rate and unidirectionality of the charge flow can be addressed. Functionalized hole conducting molecular wires of type p-oligo(phenylenevinylene) (3 aryl units, abbreviated PV3) with various anchoring groups for the covalent attachment to Co(3)O(4) catalyst nanoparticles were synthesized and two alternative methods for attachment to the oxide nanoparticle surface introduced. Covalent anchoring of intact PV3 molecules on Co(3)O(4) nanoparticles (and on SiO(2) nanoparticles for control purposes) was established by FT-Raman, FT-IR, and optical spectroscopy including observation, in some cases, of the vibrational signature of the anchored functionality. Direct monitoring of the kinetics of hole transfer from a visible light sensitizer in aqueous solution ([Ru(bpy)(3)](2+) (and derivatives) light absorber, [Co(NH(3))(5)Cl](2+) acceptor) to wire molecules on inert SiO(2)(12 nm) particles by nanosecond laser absorption spectroscopy revealed efficient, encounter controlled rates. For wire molecules anchored on Co(3)O(4) nanoparticles, the recovery of the reduced sensitizer at 470 nm indicated similarly efficient hole transfer to the attached PV3, yet no transient hole signal was detected at 600 nm. This implies hole injection from the anchored wire molecule into the Co(3)O(4) particle within 1 µs or shorter, indicating efficient charge transport from the visible light sensitizer to the oxide catalyst particle.

Time-Resolved Vibrational and Electronic Spectroscopy for Understanding How Charges Drive Metal Oxide Catalysts for Water Oxidation.

Temporally resolved spectroscopy is a powerful approach for gaining detailed mechanistic understanding of water oxidation at robust Earth-abundant metal oxide catalysts for guiding efficiency improvement of solar fuel conversion systems. Beyond detecting and structurally identifying surface intermediates by vibrational and accompanying optical spectroscopy, knowledge of how charges, sequentially delivered to the metal oxide surface, drive the four-electron water oxidation cycle is critical for enhancing catalytic efficiency. Key issues addressed in this Perspective are the experimental requirements for establishing the kinetic relevancy of observed surface species and the discovery of the rate-boosting role of encounters of two or more one-electron surface hole charges, often in the form of randomly hopping metal oxo or oxyl moieties, for accessing very low-barrier O-O bond-forming pathways. Recent spectroscopic breakthroughs of metal oxide photo- and electrocatalysts inspire future research poised to take advantage of new highly sensitive spectroscopic tools and of methods for fast catalysis triggering.

Self-Assembled Monolayers for Improved Charge Injection of Silver Back Electrodes in Inverted Organic Electronic Devices.

Self-assembled monolayers (SAMs) formed from thiol compounds bound to Ag and Au electrodes have been used as an important strategy in improving the stability and efficiency of optoelectronic devices. Thiol compounds provide only one binding site with the metal electrode which limits their influence. Dithiolane/dithiol compounds can provide multiple binding sites and could be useful in enhancing the performance of the device. In this study, inverted organic semiconducting hole-only devices were fabricated by using Ag back electrodes in conjunction with SAMs formed from disulfide lipoic acid-based compounds and were compared to a long aliphatic chain thiol. The binding and the electronic properties as well as electrical characteristics of the SAMs on silver were studied to look at the influence of their structure on charge injection in the organic semiconductor devices. It was found that the SAMs formed with (±)-α-lipoic acid, isolipoic acid, and (±)-4-phenylbutyl 5-(1,2-dithiolan-3-yl) pentanoate significantly improved the charge injection by either changing the work function of the Ag or altering the physical interaction between the polymer and the metal surface. This study may lead to an understanding of how the nature of the functional groups of the SAM and the number of bonds formed between each SAM molecule and the metal electrode influence the contact resistance and the performance of organic semiconductor devices.

Direct observation of a hydroperoxide surface intermediate upon visible light-driven water oxidation at an Ir oxide nanocluster catalyst by rapid-scan FT-IR spectroscopy.

A surface hydroperoxide intermediate has been detected upon oxidation of water at an Ir oxide nanocluster catalyst system under pulsed excitation of a [Ru(bpy)(3)](2+) visible light sensitizer by recording of the OO vibrational mode at 830 cm(-1). Rapid-scan FT-IR spectroscopy of colloidal H(2)O, D(2)O, and D(2)(18)O solutions in the attenuated total reflection mode allowed spectral assignment of IrOOH on the basis of an observed D shift of 30 cm(-1), and (18)O shifts of 24 cm(-1) ((16)O(18)O) and 46 cm(-1) ((18)O(18)O). The laser pulse response of the infrared band is consistent with the kinetic relevancy of the intermediate. This is the first observation of a surface intermediate of oxygen evolution at an Ir oxide multielectron catalyst.

Controlling and Optimizing Photoinduced Charge Transfer across Ultrathin Silica Separation Membrane with Embedded Molecular Wires for Artificial Photosynthesis.

Ultrathin amorphous silica membranes with embedded organic molecular wires (oligo(p-phenylenevinylene), three aryl units) provide chemical separation of incompatible catalytic environments of CO2 reduction and H2O oxidation while maintaining electronic and protonic coupling between them. For an efficient nanoscale artificial photosystem, important performance criteria are high rate and directionality of charge flow. Here, the visible-light-induced charge flow from an anchored Ru bipyridyl light absorber across the silica nanomembrane to Co3O4 water oxidation catalyst is quantitatively evaluated by photocurrent measurements. Charge transfer rates increase linearly with wire density, with 5 nm-2 identified as an optimal target. Accurate measurement of wire and light absorber densities is accomplished by the polarized FT-IRRAS method. Guided by density functional theory (DFT) calculations, four wire derivatives featuring electron-donating (methoxy) and -withdrawing groups (sulfonate, perfluorophenyl) with highest occupied molecular orbital (HOMO) potentials ranging from 1.48 to 0.64 V vs NHE were synthesized and photocurrents evaluated. Charge transfer rates increase sharply with increasing driving force for hole transfer from the excited light absorber to the embedded wire, followed by a decrease as the HOMO potential of the wire moves beyond the Co3O4 valence band level toward more negative values, pointing to an optimal wire HOMO potential around 1.3 V vs NHE. Comparison with photocurrents of samples without nanomembrane indicates that silica layers with optimized wires are able to approach undiminished electron flux at typical solar intensities. Combined with the established high proton conductivity and small-molecule blocking property, the charge transfer measurements demonstrate that oxidation and reduction catalysis can be efficiently integrated on the nanoscale under separation by an ultrathin silica membrane.

Advancing the frontiers in nanocatalysis, biointerfaces, and renewable energy conversion by innovations of surface techniques.

The challenge of chemistry in the 21st century is to achieve 100% selectivity of the desired product molecule in multipath reactions ("green chemistry") and develop renewable energy based processes. Surface chemistry and catalysis play key roles in this enterprise. Development of in situ surface techniques such as high-pressure scanning tunneling microscopy, sum frequency generation (SFG) vibrational spectroscopy, time-resolved Fourier transform infrared methods, and ambient pressure X-ray photoelectron spectroscopy enabled the rapid advancement of three fields: nanocatalysts, biointerfaces, and renewable energy conversion chemistry. In materials nanoscience, synthetic methods have been developed to produce monodisperse metal and oxide nanoparticles (NPs) in the 0.8-10 nm range with controlled shape, oxidation states, and composition; these NPs can be used as selective catalysts since chemical selectivity appears to be dependent on all of these experimental parameters. New spectroscopic and microscopic techniques have been developed that operate under reaction conditions and reveal the dynamic change of molecular structure of catalysts and adsorbed molecules as the reactions proceed with changes in reaction intermediates, catalyst composition, and oxidation states. SFG vibrational spectroscopy detects amino acids, peptides, and proteins adsorbed at hydrophobic and hydrophilic interfaces and monitors the change of surface structure and interactions with coadsorbed water. Exothermic reactions and photons generate hot electrons in metal NPs that may be utilized in chemical energy conversion. The photosplitting of water and carbon dioxide, an important research direction in renewable energy conversion, is discussed.