Plasmon-Induced Radical-Radical Heterocoupling Boosts Photodriven Oxidative Esterification of Benzyl Alcohol over Nitrogen-Doped Carbon-Encapsulated Cobalt Nanoparticles.

Selective oxidation of alcohols under mild conditions remains a long-standing challenge in the bulk and fine chemical industry, which usually requires environmentally unfriendly oxidants and bases that are difficult to separate. Here, a plasmonic catalyst of nitrogen-doped carbon-encapsulated metallic Co nanoparticles (Co@NC) with an excellent catalytic activity towards selective oxidation of alcohols is demonstrated. With light as only energy input, the plasmonic Co@NC catalyst effectively operates via combining action of the localized surface-plasmon resonance (LSPR) and the photothermal effects to achieve a factor of 7.8 times improvement compared with the activity of thermocatalysis. A high turnover frequency (TOF) of 15.6 h-1 is obtained under base-free conditions, which surpasses all the reported catalytic performances of thermocatalytic analogues in the literature. Detailed characterization reveals that the d states of metallic Co gain the absorbed light energy, so the excitation of interband d-to-s transitions generates energetic electrons. LSPR-mediated charge injection to the Co@NC surface activates molecular oxygen and alcohol molecules adsorbed on its surface to generate the corresponding radical species (e.g., ⋅O2 - , CH3 O⋅ and R-⋅CH-OH). The formation of multi-type radical species creates a direct and forward pathway of oxidative esterification of benzyl alcohol to speed up the production of esters.

Cost-Efficient Photovoltaic-Water Electrolysis over Ultrathin Nanosheets of Cobalt/Iron-Molybdenum Oxides for Potential Large-Scale Hydrogen Production.

Unassisted photovoltaic (PV) water splitting to hydrogen system is of great potential for future environmental-friendly fuel production from renewable solar energy. However, industrialization simultaneously requires higher efficiency, sustained stability and a lower cost for the system. In this work, the ultrathin cobalt/iron-molybdenum oxides nanosheet on nickel foam (NF) is prepared for efficient HER and OER, respectively, delivering a relatively low voltage of 1.45 V at 10 mA cm-2 in two-electrodes configuration. Water electrolysis at low voltage driven by electrocatalysts is critical for realizing energy conversion. Integrated with a commercial monocrystalline silicon cell, the H2 area specific activity of 0.47 L m-2 h-1 is achieved with a solar-to-hydrogen efficiency of 15.1% under solar simulator illumination (100 mW cm-2 ) and no performance degradation appeares over 160 h. Such a solar conversion technology demonstrates the potential for long-term and cost-efficient H2 production in large-scale industrialization and provides an exploration for new-type of energy-conversion system.

Synergetic modulation of surface alkali and oxygen vacancy over SrTiO3for the CO2photodissociation.

Photochemical conversion of CO2into solar fuels is one of the promising strategies to reducing the CO2emission and developing a sustainable carbon economy. For the more efficient utilization of solar spectrum, several approaches were adopted to pursue the visible-light-driven SrTiO3. Herein, oxygen vacancy was introduced over the commercial SrTiO3(SrTiO3-x) via the NaBH4thermal treatment, to extend the light absorption and promote the CO2adsorption over SrTiO3. Due to the mid-gap states resulted from the oxygen deficiency, combined with the intrinsic energy level of SrTiO3, the SrTiO3-xcatalyst exhibited excellent CO productivity (4.1 µmolˑg-1ˑh-1) and stability from the CO2photodissociation under the visible-light irradiation (λ > 400 nm). Then, surface alkalization over SrTiO3-x(OH-SrTiO3-x) was carried out to further enhance the CO2adsorption/activation over the surface base sites and provide the OH ions as hole acceptor, the surface alkali OH connected with Sr site of SrTiO3could also weaken the Sr-O bonding thus facilitate the regeneration of surface oxygen vacancy under the light illumination, thus resulting in 1.5 times higher CO productivity additionally. This study demonstrates that the synergetic modulation of alkali OH and oxygen vacancy over SrTiO3could largely promote the CO2photodissociation activity.

Solar-Driven Water-Gas Shift Reaction over CuOx /Al2 O3 with 1.1 % of Light-to-Energy Storage.

Hydrogen production from coal gasification provides a cleaning approach to convert coal resource into chemical energy, but the key procedures of coal gasification and thermal catalytic water-gas shift (WGS) reaction in this energy technology still suffer from high energy cost. We herein propose adopting a solar-driven WGS process instead of traditional thermal catalysis, with the aim of greatly decreasing the energy consumption. Under light irradiation, the CuOx /Al2 O3 delivers excellent catalytic activity (122 µmol gcat -1 s-1 of H2 evolution and >95 % of CO conversion) which is even more efficient than noble-metal-based catalysts (Au/Al2 O3 and Pt/Al2 O3 ). Importantly, this solar-driven WGS process costs no electric/thermal power but attains 1.1 % of light-to-energy storage. The attractive performance of the solar-driven WGS reaction over CuOx /Al2 O3 can be attributed to the combined photothermocatalysis and photocatalysis.

Constructing Solid-Gas-Interfacial Fenton Reaction over Alkalinized-C3N4 Photocatalyst To Achieve Apparent Quantum Yield of 49% at 420 nm.

Efficient generation of active oxygen-related radicals plays an essential role in boosting advanced oxidation process. To promote photocatalytic oxidation for gaseous pollutant over g-C3N4, a solid-gas interfacial Fenton reaction is coupled into alkalinized g-C3N4-based photocatalyst to effectively convert photocatalytic generation of H2O2 into oxygen-related radicals. This system includes light energy as power, alkalinized g-C3N4-based photocatalyst as an in situ and robust H2O2 generator, and surface-decorated Fe3+ as a trigger of H2O2 conversion, which attains highly efficient and universal activity for photodegradation of volatile organic compounds (VOCs). Taking the photooxidation of isopropanol as model reaction, this system achieves a photoactivity of 2-3 orders of magnitude higher than that of pristine g-C3N4, which corresponds to a high apparent quantum yield of 49% at around 420 nm. In-situ electron spin resonance (ESR) spectroscopy and sacrificial-reagent incorporated photocatalytic characterizations indicate that the notable photoactivity promotion could be ascribed to the collaboration between photocarriers (electrons and holes) and Fenton process to produce abundant and reactive oxygen-related radicals. The strategy of coupling solid-gas interfacial Fenton process into semiconductor-based photocatalysis provides a facile and promising solution to the remediation of air pollution via solar energy.

Metal-organic frameworks for photocatalysis.

Photocatalysis is a promising technology to convert solar energy into chemical energy. Recently, metal-organic frameworks (MOFs) have emerged as novel photocatalysts owing to their inherent structural characteristics of a large surface area and a well-ordered porous structure. Most importantly, via modulation of the organic linker/metal clusters or incorporation with metal/complex catalysts, not only the reactant adsorption and light absorption but also the charge separation and reactant activation will be largely promoted, leading to superior photocatalytic performance. In this article, we will first introduce the photophysical/chemical properties of MOFs; then various strategies of modification of MOFs towards better photocatalytic activity will be presented; finally, we will address the challenge and further perspective in MOF-based photocatalysis.

Effect of band structure on the hot-electron transfer over Au photosensitized brookite TiO2.

Au photosensitization can endow TiO2 visible-light-driven photocatalytic properties. Herein, via facet-optimized brookite TiO2 with tunable electronic band structures as the substrate, we found that intense visible light excitation of Au will result in the accumulation of hot-electrons, which will negatively shift the EF of Au and lower the Schottky barrier, thus ensuring their consecutive injections into the CB of TiO2; in this case, hot-electrons with more reduction potential will lead to superior photocatalytic activity.

Porous-structured Cu2O/TiO2 nanojunction material toward efficient CO2 photoreduction.

Porous-structured Cu2O/TiO2 nanojunction material is successfully fabricated by a facile method via loading Cu2O nanoparticles on the network of a porous TiO2 substrate. The developed Cu2O/TiO2 nanojunction material has a size of several nanometers, in which the p-type Cu2O and n-type TiO2 nanoparticles are closely contacted with each other. The well designed nanojunction structure is beneficial for the charge separation in the photocatalytic reaction. Meanwhile, the porous structure of the Cu2O/TiO2 nanojunction can facilitate the CO2 adsorption and offer more reaction active sites. Most importantly, the gas-phase CO2 photoreduction tests reveal that our developed porous-structured Cu2O/TiO2 nanojunction material exhibits marked photocatalytic activity in the CH4 evolution, about 12, 9, and 7.5 times higher than the pure TiO2, Pt-TiO2, and commercial Degussa P25 TiO2 powders, respectively. The greatly enhanced activity can be attributed to the well designed nanojunction structure combined with the porous structure, which can simultaneously enhance the charge separation efficiency and facilitate the CO2 adsorption.

Robust block sparse discriminative classification framework.

In this paper, a block sparse discriminative classification framework (BSDC) is proposed under the assumption that a block or group structure exists in sparse coefficients on classification. First, we propose a block discriminative dictionary-learning (BDDL) algorithm, which learns class-specific subdictionaries and forces the sparse coefficients to be block sparse. An efficient gradient-based optimization strategy of BDDL also is developed, and the block sparse constraint of the sparse coefficient leads to a least-squares solution of nonzero entries in the sparse coding stage of dictionary learning. Second, to take advantage of the structures when a new test sample is given, conventional sparse coding algorithms are discarded, and structured sparse coding methods are adopted. Experiments validate the effectiveness of the proposed framework in face recognition and texture classification. We also show that BSDC is robust to noise.

Photothermal conversion of CO2 into CH4 with H2 over Group VIII nanocatalysts: an alternative approach for solar fuel production.

The photothermal conversion of CO2 provides a straightforward and effective method for the highly efficient production of solar fuels with high solar-light utilization efficiency. This is due to several crucial features of the Group VIII nanocatalysts, including effective energy utilization over the whole range of the solar spectrum, excellent photothermal performance, and unique activation abilities. Photothermal CO2 reaction rates (mol h(-1) g(-1)) that are several orders of magnitude larger than those obtained with photocatalytic methods (µmol h(-1) g(-1)) were thus achieved. It is proposed that the overall water-based CO2 conversion process can be achieved by combining light-driven H2 production from water and photothermal CO2 conversion with H2. More generally, this work suggests that traditional catalysts that are characterized by intense photoabsorption will find new applications in photo-induced green-chemistry processes.

Unleashing the Full Potential of Photo-Driven CO Hydrogenation to Light Olefins over Carbon-Coated CoMn-Based Catalysts.

As a nonpetroleum process, photodriven Fischer-Tropsch synthesis provides a practical approach for the synthesis of light olefins. However, maximizing the solar-energy conversion efficiency based on the design of the composite catalyst and understanding the catalytic mechanism remain challenging. Herein, a novel carbon-coated CoMn-based catalyst, a C-coated mixture of Co and MnO, is designed for the efficient conversion of syngas to light olefins under light irradiation. The CoMnC-450 catalyst exhibits a CO conversion of 12.6% with a selectivity to light olefins of 36.5% under light irradiation, showing 5.5-fold the activity of thermocatalysis. Experimental characterizations as certain the CoMnC-450 catalyst can be excited to generate photogenerated carriers under light irradiation and then the electron transfer to metallic Co to form electron-rich active sites with carbon mediation, thereby enhancing the catalytic performance. In situ Fourier transform infrared spectroscopy and theoretical calculation based on density functional theory reveal the unique roles of photogenerated carriers in promoting the adsorption and activation of CO molecules. This study demonstrates a feasible catalyst model to efficiently utilize full-spectral solar light to produce the value-added chemical.

{Ta12}/{Ta16} cluster-containing polytantalotungstates with remarkable photocatalytic H2 evolution activity.

Four novel polytantalotungstates K(5)Na(4)[P(2)W(15)O(59)(TaO(2))(3)]·17H(2)O (1), K(8)Na(8)H(4)[P(8)W(60)Ta(12)(H(2)O)(4)(OH)(8)O(236)]·42H(2)O (2), Cs(3)K(3.5)H(0.5)[SiW(9)(TaO(2))(3)O(37)]·9H(2)O (3), and Cs(10.5)K(4)H(5.5)[Ta(4)O(6)(SiW(9)Ta(3)O(40))(4)]·30H(2)O (4) were synthesized. Compounds 1 and 3 are tris-(peroxotantalum)-substituted Dawson- and Keggin-type derivatives, whereas 2 and 4 are tetrameric oligomers containing respectively an unprecedented {Ta(12)} and {Ta(16)} cluster core. The photocatalytic activities of 2 and 4 for H(2) evolution from water were evaluated. The significantly enhanced performance against the control K(6)[P(2)W(18)O(62)] can be attributed to the modulation of the electronic structures of these novel POMs by Ta incorporation. The highest activity observed so far with the use of 2 can be further rationalized by the presence of distorted heptacoordinate Ta atoms in the form of TaO(7) pentagonal bipyramid.

Surface-alkalinization-induced enhancement of photocatalytic H2 evolution over SrTiO3-based photocatalysts.

A strategy of reaction-environment modulation was employed to change the surface property of a semiconductor photocatalyst to enhance its photocatalytic performance. Surface alkalinization induced by a high alkalinity of the solution environment significantly shifted the surface energy band of a SrTiO(3) photocatalyst to a more negative level, supplying a strong potential for H(2)O reduction and consequently promoting the photocatalytic efficiency of H(2) evolution. This mechanism is also applicable for visible-light-sensitive La,Cr-codoped SrTiO(3) photocatalyst, which hence, could achieve a high apparent quantum efficiency of 25.6% for H(2) evolution in CH(3)OH aqueous solution containing 5 M NaOH at an incident wavelength of 425 ± 12 nm.

Selective growth of metallic Ag nanocrystals on Ag3PO4 submicro-cubes for photocatalytic applications.

Thinking outside the box: The position- and number-selective growth of Ag nanocrystals on Ag(3)PO(4) submicro-cubes by an in situ reduction technique is demonstrated (see figure). These new Ag/Ag(3)PO(4) heterocubes exhibit higher photocatalytic activities than pure Ag(3)PO(4) cubes for the degradation of organic dyes under visible-light irradiation.

Site-selected doping of upconversion luminescent Er3+ into SrTiO3 for visible-light-driven photocatalytic H2 or O2 evolution.

A series of upconversion luminescent erbium-doped SrTiO(3) (ABO(3)-type) photocatalysts with different initial molar ratios of Sr/Ti have been prepared by a facile polymerized complex method. Er(3+) ions, which were gradually transferred from the A to the B site with increasing Sr/Ti, enabled the absorption of visible light and the generation of high-energy excited states populated by upconversion processes. The local internal fields arising from the dipole moments of the distorted BO(6) octahedra promoted energy transfer from the high-energy excited states of Er(3+) with B-site occupancy to the host SrTiO(3) and thus enhanced the band-to-band transition of the host SrTiO(3). Consequently, the erbium-doped SrTiO(3) species with B-site occupancy showed higher photocatalytic activity than those with A-site occupancy for visible-light-driven H(2) or O(2) evolution in the presence of the corresponding sacrificial reagents. The results generally suggest that the introduction of upconversion luminescent agents into host semiconductors is a promising approach to simultaneously harnessing low-energy photons and maintaining redox ability for photocatalytic H(2) and O(2) evolution and that the site occupancy of doped elements in ABO(3)-type perovskite oxides greatly determines the photocatalytic activity.

Mechanism of photocatalytic activities in Cr-doped SrTiO3 under visible-light irradiation: an insight from hybrid density-functional calculations.

We used hybrid density-functional calculations to clarify the effect of substituting chromium for titanium (Cr(Ti)) on photocatalytic activities of Cr-doped SrTiO(3). A singly negative Cr(Ti)⁻, which is relevant to a lower oxidation state of Cr, is advantageous for the visible light absorption without forming electron trapping centers, while other charge states are inactive for the photocatalytic reaction. Stabilizing the desirable charge state (Cr(Ti)⁻) is feasible by shifting the Fermi level towards the conduction band. Our theory sheds light on the photocatalytic properties of metal-doped semiconductors.

Photoassisted fabrication of zinc indium oxide/oxysulfide composite for enhanced photocatalytic H2 evolution under visible-light irradiation.

A photoassisted approach has been developed to synthesize a zinc indium oxide (Zn5In2O8)/oxysulfide composite through in situ sulfuration of vacancy-rich Zn5In2O8. It was found that vacancies have a considerable impact on the formation of the composite. The composite exhibited an increased photocatalytic H2 evolution activity under visible-light irradiation, which probably resulted from the enhanced ability to separate photoinduced electrons and holes. The H2 evolution rate over the composite was about 17 times higher when using vacancy-rich rather than conventional Zn5In2O8. This study provides a new method of improving the activity of photocatalysts.

Photothermal synthesis of a CuO x &FeO y catalyst with a layered double hydroxide-derived pore-confined frame to achieve photothermal CO2 hydrogenation to CO with a rate of 136 mmol min-1 gcat -1.

Solar-driven CO2 conversion into the industrial chemical CO via the reverse water-gas reaction is an ideal technological approach to achieve the key step of carbon neutralization. The high reaction temperature is cost-free due to the photothermal conversion brought about by solar irradiation and is beneficial to the catalytic efficiency. However, the thermostability of adopted catalysts is a great challenge. Herein, we develop an in situ photothermal synthesis to obtain a CuO x &FeO y catalyst with a layered double hydroxide-derived pore-confined frame. The optimized sample delivers a CO generation rate of 136.3 mmol min-1 gcat -1 with the selectivity of ∼100% at a high reaction temperature of 1015 °C. The efficient catalytic activity can be attributed to the fact that the pore-confined frame substrate prevents the growth of CuO x and FeO y nanoparticles during the high-temperature reaction and the basic groups on the substrate promote the adsorption and activation of CO2.

Subsurface oxygen defects electronically interacting with active sites on In2O3 for enhanced photothermocatalytic CO2 reduction.

Oxygen defects play an important role in many catalytic reactions. Increasing surface oxygen defects can be done through reduction treatment. However, excessive reduction blocks electron channels and deactivates the catalyst surface due to electron-trapped effects by subsurface oxygen defects. How to effectively extract electrons from subsurface oxygen defects which cannot directly interact with reactants is challenging and remains elusive. Here, we report a metallic In-embedded In2O3 nanoflake catalyst over which the turnover frequency of CO2 reduction into CO increases by a factor of 866 (7615 h-1) and 376 (2990 h-1) at the same light intensity and reaction temperature, respectively, compared to In2O3. Under electron-delocalization effect of O-In-(O)Vo-In-In structural units at the interface, the electrons in the subsurface oxygen defects are extracted and gather at surface active sites. This improves the electronic coupling with CO2 and stabilizes intermediate. The study opens up new insights for exquisite electronic manipulation of oxygen defects.

ß-AgAl(1-x)Ga(x)O2 solid-solution photocatalysts: continuous modulation of electronic structure toward high-performance visible-light photoactivity.

A series of ß-AgAl(1-x)Ga(x)O(2) solid-solution materials were explored as novel visible-light-sensitive photocatalysts. These Ag-based solid solutions crystallize in a homogeneous crystal structure with orthorhombic symmetry but possess continuously modulated band gaps from 2.19 to 2.83 eV by decreasing the ratios of Ga/Al. Their photoactivities for iso-propanol degradation were found to be dependent on the variation of chemical compositions. Among them, the ß-AgAl(0.6)Ga(0.4)O(2) sample showed the highest photocatalytic performance, which simultaneously exhibited 35 and 63 times higher activities than two terminus materials, ß-AgAlO(2) and ß-AgGaO(2), respectively. The apparent quantum efficiency of this sample for iso-propanol photodegradation achieved up to 37.3% at the wavelength of 425 ± 12 nm. The theoretical calculation based on density functional theory demonstrated that the levels of valence band maximum of ß-AgAl(1-x)Ga(x)O(2) are similar, but the levels of conduction band minimum are gradually negatively shifted with the increase of the ratio of Ga/Al, thereby continuously narrowing the band gap. Nevertheless, the highest activity observed on ß-AgAl(0.6)Ga(0.4)O(2) may be attributed to its optimized band structure, which adapts the balance between effective visible-light absorption and adequate redox potentials.