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.

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.

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.

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.

Structural and Componential Engineering of Co2P&CoP@N-C Nanoarrays for Energy-Efficient Hydrogen Production from Water Electrolysis.

The development of electrocatalysts for efficient water splitting is a pivotal and challenging task. Transition-metal phosphides (TMPs) have been known as one of the most promising candidates for the efficient hydrogen evolution reaction (HER) due to their favorable intrinsic reactivity. However, structural engineering related to the gas bubbles evolution and tiny regulation of components concerned with the electronic structure remained as a significant challenge that requires further optimization. Herein, the nanoarrays (NAs) composed of ultrasmall Co2P and CoP nanoparticle-embedded N-doped carbon matrix (Co2P&CoP@N-C) are prepared and demonstrated an overpotential of 62.8 ± 4.7 mV at 10 mA cm-2 in 1.0 M KOH. The nanoarray-structured electrocatalyst revealed the superaerophobicity and facilitates the detachment of the in situ formed hydrogen gas bubbles, ensuring abundant catalytic sites and electrode-electrolyte interface for the mass transfer process. The amount of P doping modulated the local electron density around Co and P atoms, which attains a favorable compromise to afford sufficient electrons for the electrocatalysis and inhibit the negative influence of H2 desorption. Significantly, the lowered overpotential induced by the electrocatalyst surface architecture is much stronger than that of the component content and promotes the electrocatalytic activity.

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.

CoAl-layered double hydroxide nanosheet-based fluorescence assay for fast DNA detection.

In the study, CoAl-layered double hydroxide (CoAl-LDH) was prepared as a fluorescence quenching agent to detect DNA molecules. Because of its simple preparation for a large scale, excellent surface effect, good biocompatibility and high fluorescence quenching capability, the effective, rapid, and sensitive DNA detection was realized. The fluorescence quenching efficiency of LDH to 5(6)-carboxyfluorescein attached to single stranded DNA (FAM-ssDNA) was as high as 88%, and after FAM-ssDNA hybridized with the complementary DNA oligonucleotide, that to FAM-dsDNA was about 33%. The quenching mechanisms of LDH for ssDNA and dsDNA were discussed. Phosphate exposed of ssDNA played an important role in quenching effect. Compared to dsDNA, more exposed phosphate groups in ssDNA resulted in the stronger electrostatic interaction between ssDNA and LDH, and thus the higher quenching efficiency. Under optimal conditions, the linear equation was y = 38.26 + 3.37x in a linear relationship of 1-50 nM, and the correlation coefficient R2 corresponded to 0.999, and the limit of detection was calculated to be 0.79 nM (3σ). Cytotoxicity studies have shown that LDH has good biocompatibility. The study provides an effective, sensitive and safe approach for DNA detection and gives an insight for the design of LDH-based biosensing materials.

Modulation of an intermediate layer between NiCoP and Ni foam substrate in a microwire array electrode for enhancing the hydrogen-evolution reaction.

A hierarchical electrode consisting of a Ni foam substrate, an intermediate layer of a Mo-doped basic cobalt carbonate microwire array, and a surface layer of NiCoP was fabricated for hydrogen evolution. The introduction of the intermediate layer accounted for the low overpotential (45 mV, 10 mA cm-2) and high solar-to-hydrogen conversion efficiency (14.9%) in a PEC water splitting application.

Photoinduced Defect Engineering: Enhanced Photothermal Catalytic Performance of 2D Black In2 O3- x Nanosheets with Bifunctional Oxygen Vacancies.

Photothermal CO2 reduction technology has attracted tremendous interest as a solution for the greenhouse effect and energy crisis, and thereby it plays a critical role in solving environmental problems and generating economic benefits. In2 O3- x has emerged as a potential photothermal catalyst for CO2 conversion into CO via the light-driven reverse water gas shift reaction. However, it is still a challenge to modulate the structural and electronic characteristics of In2 O3 to enhance photothermocatalytic activity synergistically. In this work, a novel route to activate inert In(OH)3 into 2D black In2 O3- x nanosheets via photoinduced defect engineering is proposed. Theoretical calculations and experimental results verify the existence of bifunctional oxygen vacancies in the 2D black In2 O3- x nanosheets host, which enhances light harvesting and chemical adsorption of CO2 molecules dramatically, achieving 103.21 mmol gcat -1 h-1 with near-unity selectivity for CO generation and meanwhile excellent stability. This study reveals an exciting phenomenon that light is an ideal external stimulus on the layered In2 O3 system, and its electronic structure can be adjusted efficiently through photoinduced defect engineering; it can be anticipated that this synthesis strategy can be extended to wider application fields.

Bifunctional hydroxyl group over polymeric carbon nitride to achieve photocatalytic H2O2 production in ethanol aqueous solution with an apparent quantum yield of 52.8% at 420 nm.

A photocatalytic system of carbon nitride grafted with hydroxyl groups working in ethanol aqueous solution under visible light irradiation was constructed to simultaneously achieve photocatalytic H2O2 production with an apparent quantum efficiency of 52.8% at around 420 nm and ethanol conversion to high-value acetaldehyde with a high selectivity of 99.95%.

Co and Fe Codoped WO2.72 as Alkaline-Solution-Available Oxygen Evolution Reaction Catalyst to Construct Photovoltaic Water Splitting System with Solar-To-Hydrogen Efficiency of 16.9.

Oxygen evolution electrode is a crucial component of efficient photovoltaic-water electrolysis systems. Previous work focuses mainly on the effect of electronic structure modulation on the oxygen evolution reaction (OER) performance of 3d-transition-metal-based electrocatalyst. However, high-atomic-number W-based compound with complex electronic structure for versatile modulation is seldom explored because of its instability in OER-favorable alkaline solution. Here, codoping induced electronic structure modulation generates a beneficial effect of transforming the alkaline-labile WO2.72 (WO) in to efficient alkaline-solution-stable Co and Fe codoped WO2.72 (Co&Fe-WO) with porous urchin-like structure. The codoping lowers the chemical valence of W to ensure the durability of W-based catalyst, improves the electron-withdrawing capability of W and O to stabilize the Co and Fe in OER-favorable high valence state, and enriches the surface hydroxyls, which act as reactive sites. The Co&Fe-WO shows ultralow overpotential (226 mV, J = 10 mA cm-2), low Tafel slope (33.7 mV dec-1), and good conductivity. This catalyst is finally applied to a photovoltaic-water splitting system to stably produce hydrogen for 50 h at a high solar-to-hydrogen efficiency of 16.9%. This work highlights the impressive effect of electronic structure modulation on W-based catalyst, and may inspire the modification of potential but unstable catalyst for solar energy conversion.

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.

Synergistic Activity of Co and Fe in Amorphous Cox-Fe-B Catalyst for Efficient Oxygen Evolution Reaction.

Water splitting has been greatly limited by the sluggish kinetics of the oxygen evolution reaction (OER). High-oxidation-state metal species are required as the favorable active sites in OER. Here, amorphous Cox-Fe-B (x is the molar ratio of Co/Fe), Co-B, and Fe-B compounds were successfully synthesized as the oxygen evolution electrocatalysts. The calculation of turnover frequency (TOF) indicates that both the Co and Fe sites are active for OER. Cyclic voltammetry, X-ray photoelectron spectroscopy, and long-term stability curves were used to demonstrate that Fe can stabilize Co in a higher oxidation level and meanwhile promote the generation of OOH-like species (the key intermediates for OER). The reduced impedance for Co2-Fe-B (compared with that for Fe-B and Co-B) obtained from the electrochemical impedance spectra confirms the enhanced conductivity for the Co2-Fe-B. This optimal sample on Cu substrate shows a low overpotential of 0.298 V at the current density of 10 mA cm-2 with a decreased overpotential of 42 mV compared to that of Co-B. The Co2-Fe-B catalyst also exhibits a small Tafel slope of 62.6 mV/dec and good stability. The enhanced performance could be attributed to the synergistic effect of the increased population of high-oxidation-state metal-OOH species and the promoted conductivity of the catalyst. A solar-to-hydrogen energy conversion efficiency of 4.2% and a Faradaic efficiency of 97.2% can be achieved by connecting the HER and as-prepared OER electrodes to a crystalline silicon solar cell.

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.

Nanometals for Solar-to-Chemical Energy Conversion: From Semiconductor-Based Photocatalysis to Plasmon-Mediated Photocatalysis and Photo-Thermocatalysis.

Nanometal materials play very important roles in solar-to-chemical energy conversion due to their unique catalytic and optical characteristics. They have found wide applications from semiconductor photocatalysis to rapidly growing surface plasmon-mediated heterogeneous catalysis. The recent research achievements of nanometals are reviewed here, with regard to applications in semiconductor photocatalysis, plasmonic photocatalysis, and plasmonic photo-thermocatalysis. As the first important topic discussed here, the latest progress in the design of nanometal cocatalysts and their applications in semiconductor photocatalysis are introduced. Then, plasmonic photocatalysis and plasmonic photo-thermocatalysis are discussed. A better understanding of electron-driven and temperature-driven catalytic behaviors over plasmonic nanometals is helpful to bridge the present gap between the communities of photocatalysis and conventional catalysis controlled by temperature. The objective here is to provide instructive information on how to take the advantages of the unique functions of nanometals in different types of catalytic processes to improve the efficiency of solar-energy utilization for more practical artificial photosynthesis.

Synergistic effect of Au and Rh on SrTiO3 in significantly promoting visible-light-driven syngas production from CO2 and H2O.

A novel photocatalyst constructed by Rh, Au, and SrTiO3 was developed to realize syngas photosynthesis from low-cost CO2 and H2O feedstock under visible-light irradiation. The synergistic effect of Rh and Au on SrTiO3 contributed to a 22- and 153-fold photoactivity magnification for syngas yield in contrast to Au@SrTiO3 and Rh@SrTiO3 samples, respectively.

Designing Au Surface-Modified Nanoporous-Single-Crystalline SrTiO3 to Optimize Diffusion of Surface Plasmon Resonance-Induce Photoelectron toward Enhanced Visible-Light Photoactivity.

Nanoporous single-crystalline SrTiO3 is fabricated at a low temperature of 60 °C via a novel approach of sol-gel alkali-dissolution-exothermal reaction. The plasmon-active metal Au is loaded on the nanoporous single-crystalline SrTiO3 material to construct a new kind of plasmonic photocatalyst. Due to the single-crystalline nature and the space confinement effect of pores for Au growing, not only the promoted diffusion efficiency of surface plasmon resonance (SPR)-induce photoelectron is achieved, but also the diffusion region are well optimized via changing the loading amount of Au. Therefore, an optimal sample with 4.8 wt % Au loading exhibits a more than 40-fold photoactivity enhancement under visible-light irradiation compared to the common nanosized SrTiO3 (a commercially available sample) loaded with 5.3 wt % Au which was prepared under the same condition. Furthermore, combining the special nanostructure of Au surface-modified nanoporous-single-crystalline SrTiO3 with photocatalytic properties, estimation of the diffusion mean free path of SPR-induce photoelectron can be achieved. This study proposes an alternative approach to enhance the photoactivity of plasmonic photocatalyst via fine designing the semiconductor substrate.

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.

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.