Boosted Sacrificial-Agent-Free Selective Photoreduction of CO2 to CH3OH by Rhenium Atomically Dispersed on Indium Oxide.

Solar-energy-driven photoreduction of CO2 is promising in alleviating environment burden, but suffers from low efficiency and over-reliance on sacrificial agents. Herein, rhenium (Re) is atomically dispersed in In2O3 to fabricate a 2Re-In2O3 photocatalyst. In sacrificial-agent-free photoreduction of CO2 with H2O, 2Re-In2O3 shows a long-term stable efficiency which is enhanced by 3.5 times than that of pure In2O3 and is also higher than those on Au-In2O3, Ag-In2O3, Cu-In2O3, Ir-In2O3, Ru-In2O3, Rh-In2O3 and Pt-In2O3 photocatalysts. Moreover, carbon-based product of the photoreduction overturns from CO on pure In2O3 to CH3OH on 2Re-In2O3. Re promotes charge separation, H2O dissociation and CO2 activation, thus enhancing photoreduction efficiency of CO2 on 2Re-In2O3. During the photoreduction, CO is a key intermediate. CO prefers to desorption rather than hydrogenation on pure In2O3, as CO binds to pure In2O3 very weakly. Re strengthens the interaction of CO with 2Re-In2O3 by 5.0 times, thus limiting CO desorption but enhancing CO hydrogenation to CH3OH. This could be the origin for photoreduction product overturn from CO on pure In2O3 to CH3OH on 2Re-In2O3. The present work opens a new way to boost sacrificial-agent-free photoreduction of CO2.

Electronic Interactions on Platinum/(Metal-Oxide)-Based Photocatalysts Boost Selective Photoreduction of CO2 to CH4.

By supporting platinum (Pt) and cadmium sulfide (CdS) nanoparticles on indium oxide (In2 O3 ), we fabricated a CdS/Pt/In2 O3 photocatalyst. Selective photoreduction of carbon dioxide (CO2 ) to methane (CH4 ) was achieved on CdS/Pt/In2 O3 with electronic Pt-In2 O3 interactions, with CH4 selectivity reaching to 100 %, which is higher than that on CdS/Pt/In2 O3 without electronic Pt-In2 O3 interactions (71.7 %). Moreover, the enhancement effect of electronic Pt-(metal-oxide) interactions on selective photoreduction of CO2 to CH4 also occurs by using other common metal oxides, such as photocatalyst supports, including titanium oxide, gallium oxide, zinc oxide, and tungsten oxide. The electronic Pt-(metal-oxide) interactions separate photogenerated electron-hole pairs and convert CO2 into CO2 δ- , which can be easily hydrogenated into CH4 via a CO2 δ- →HCOO*→HCO*→CH*→CH4 path, thus boosting selective photoreduction of CO2 to CH4 . This offers a new way to achieve selective photoreduction of CO2 .

Long-Term Stable Hydrogen Production from Water and Lactic Acid via Visible-Light-Driven Photocatalysis in a Porous Microreactor.

Photocatalytic hydrogen (H2 ) production is significant to overcome challenges like fossil fuel depletion and carbon dioxide emission, but its efficiency is still far below that which is needed for commercialization. Herein, we achieve long-term stable H2 bubbling production from water (H2 O) and lactic acid via visible-light-driven photocatalysis in a porous microreactor (PP12); the catalytic system benefits from photocatalyst dispersion, charge separation, mass transfer, and dissociation of O-H bonds associated with H2 O. With the widely used platinum/cadmium-sulfide (Pt/CdS) photocatalyst, PP12 leads to a H2 bubbling production rate of 602.5 mmol h-1 m-2 , which is 1000 times higher than that in a traditional reactor. Even when amplifying PP12 into a flat-plate reactor with an area as large as 1 m2 and extending the reaction time to 100 h, the H2 bubbling production rate still remains at around 600.0 mmol h-1 m-2 , offering great potential for commercialization.

Efficient Removal of Pb2+ from Water by Bamboo-Derived Thin-Walled Hollow Ellipsoidal Carbon-Based Adsorbent.

Lead ion (Pb2+) is one of the most common water pollutants. Herein, with bamboo as the raw material, we fabricate a thin-walled hollow ellipsoidal carbon-based adsorbent (CPCs900) containing abundant O-containing groups and carbon defects and having a specific surface area as large as 730.87 m2 g-1. CPCs900 shows a capacity of 37.26 mg g-1 for adsorbing Pb2+ in water and an efficiency of 98.13% for removing Pb2+ from water. This is much better than the activated carbon commonly used for removing Pb2+ from water (12.19 mg g-1, 30.48%). The bond interaction of Pb2+ with the O-containing groups on CPCs900 and the electrostatic interaction of Pb2+ with the electron-rich carbon defects on CPCs900 could be the main forces to drive Pb2+ adsorption on CPCs900. The outstanding adsorption performance of CPCs900 could be due to the abundant O-containing groups and carbon defects as well as the large specific surface area of CPCs900. Bamboo has a large reserve and a low price. The present work successfully converts bamboo into adsorbents with outstanding performances in removing Pb2+ from water. This is of great significance for meeting the huge industrial demand on highly efficient adsorbents for removing toxic metal ions from water.

Fast and efficient electrocatalytic oxidation of glucose triggered by Cu2O-CuO nanoparticles supported on carbon nanotubes.

Electrocatalytic glucose oxidation reaction (GOR) is the key to construct sophisticated devices for fast and accurately detecting trace glucose in blood and food. Herein, a noble-metal-free Cu/C-60 catalyst is fabricated by supporting Cu2O-CuO nanoparticles on carbon nanotubes through a novel discharge process. For GOR, Cu/C-60 shows a sensitivity as high as 532 µA mM-1 cm-2, a detection limit as low as 1 µM and a steady-state response time of only 5.5 s. Moreover, Cu/C-60 has outstanding stability and anti-interference ability to impurities. The synergistic effect of Cu2O-CuO could improve the adsorption and conversion of glucose, thus enhancing GOR performance. By using Cu/C-60, we fabricate a three-electrode chip. A portable and compact electrochemical system is constructed by connecting the three-electrode chip with Cu/C-60 to an integrated circuit board and a mobile phone for recording and displaying data. The portable and compact electrochemical system results in a GOR sensitivity of 501 µA mM-1 cm-2, which is close to the data measured on the bloated electrochemical workstation. The detection limit of the portable and compact electrochemical system in GOR is 50 µM. This is higher than those obtained on the bloated electrochemical workstation, but is much lower than the common blood glucose concentration of human body (>3 mM). This demonstrates the accuracy, reasonability and applicability of the portable and compact electrochemical system. The results of the present work are helpful for fabricating fast, efficient and portable devices for detecting trace amount of glucose in blood and food.

Boosting photoelectrochemical efficiency by near-infrared-active lattice-matched morphological heterojunctions.

Photoelectrochemical catalysis is an attractive way to provide direct hydrogen production from solar energy. However, solar conversion efficiencies are hindered by the fact that light harvesting has so far been of limited efficiency in the near-infrared region as compared to that in the visible and ultraviolet regions. Here we introduce near-infrared-active photoanodes that feature lattice-matched morphological hetero-nanostructures, a strategy that improves energy conversion efficiency by increasing light-harvesting spectral range and charge separation efficiency simultaneously. Specifically, we demonstrate a near-infrared-active morphological heterojunction comprised of BiSeTe ternary alloy nanotubes and ultrathin nanosheets. The heterojunction's hierarchical nanostructure separates charges at the lattice-matched interface of the two morphological components, preventing further carrier recombination. As a result, the photoanodes achieve an incident photon-to-current conversion efficiency of 36% at 800 nm in an electrolyte solution containing hole scavengers without a co-catalyst.

Incorporating MoO3 Patches into a Ni Oxyhydroxide Nanosheet Boosts the Electrocatalytic Oxygen Evolution Reaction.

The electrocatalytic oxygen evolution reaction from H2O (OER) is essential in a number of areas like electrocatalytic hydrogen production from H2O. A Ni oxyhydroxide nanosheet (NiNS) is among the most widely studied OER catalysts but still suffers from low activity, sluggish kinetics, and poor stability. Herein, we incorporate MoO3 patches into NiNS to form a nanosheet with an intimate Ni-Mo interface (NiMoNS) for the OER. The overpotential at 10 mA cm-2 and Tafel slope on NiMoNS (260 mV, 54.7 mV dec-1) are lower than those on NiNS (296 mV, 89.3 mV dec-1), implying that higher activity and faster kinetics are achieved on NiMoNS. There is no change in electrocatalytic efficiency of NiMoNS after 18 h of OER, but the electrocatalytic efficiency of NiNS decreases by 56% after only 8 h of OER. Thus, NiMoNS has better stability. The intimate Ni-Mo interface promotes two-dimensional lateral growth of NiMoNS to form a surface area 1.5 times larger than that of NiNS, and facilitates electron transfer from Ni to Mo. This makes the Ni3+/Ni2+ ratio on the NiMoNS surface (1.32) higher than that on the NiNS surface (0.68). Moreover, the Ni3+/Ni2+ ratio on NiMoNS surface increases to 1.81 after 18 h of OER but the Ni3+/Ni2+ ratio on the NiNS surface decreases to 0.51 after 8 h of OER. Therefore, the NiMoNS surface has more abundant and stable Ni3+ sites which are catalytically active toward OER. This could be the reason for the enhanced activity, kinetics, and stability of NiMoNS. The results are very valuable for fabricating more efficient catalysts for electrocatalysis.

Carbon-Coated Tungsten Oxide Nanospheres Triggering Flexible Electron Transfer for Efficient Electrocatalytic Oxidation of Water and Glucose.

Electrocatalytic oxidation of water (i.e., oxygen evolution reaction, OER) plays crucial roles in energy, environment, and biomedicine. It is a key factor affecting the efficiencies of electrocatalytic reactions conducted in aqueous solution, e.g., electrocatalytic water splitting and glucose oxidation reaction (GOR). However, electrocatalytic OER still suffers from problems like high overpotential, sluggish kinetics, and over-reliance on expensive noble-metal-based catalysts. Herein, 15 nm thick carbon-based shell coated tungsten oxide (CTO) nanospheres are loaded on nickel foam to form CTO/NF. An enhanced electrocatalytic OER is triggered on CTO/NF, with the overpotential at 50 mA cm-2 (317 mV) and the Tafel slope (70 mV dec-1) on CTO/NF lower than those on pure tungsten oxide (360 mV, 117 mV dec-1) and noble-metal-based IrO2 catalysts (328 mV, 96 mV dec-1). A promoted electrocatalytic GOR is also achieved on CTO/NF, with efficiency as high as 189 µA mM-1 cm-2. The carbon-based shell on CTO is flexible for electron transfer between catalyst and reactants and provides catalytically active sites. This improves reactant adsorption and O-H bond dissociation on the catalyst, which are key steps in OER and GOR. The carbon-based shell on CTO retains the catalyst as nanospheres with a higher surface area, which facilitates OER and GOR. It is the multiple roles of the carbon-based shell that increases the electrocatalytic efficiency. These results are helpful for fabricating more efficient noble-metal-free electrocatalysts.

Noble-Metal-Free CdS Nanoparticle-Coated Graphene Oxide Nanosheets Favoring Electron Transfer for Efficient Photoreduction of CO2.

Graphene oxide (GO) nanosheets are promising noble-metal-free catalysts. However, the catalytic activity and selectivity of GO are still very low. Herein, GO is first functionalized via noncovalent interactions by an aspartic acid modified anhydride having COOH groups to form A-GO. A-GO is more conductive and hydrophilic than GO and P-GO synthesized via functionalizing GO by a COOH-free anhydride. Then, we load CdS nanoparticles, which are responsible for absorbing light to produce charge carriers, on A-GO to fabricate a CdS/A-GO photocatalyst without noble metals for the photoreduction of CO2 by H2O. CdS/A-GO exhibits a higher photoreduction efficiency than that of CdS/GO and CdS/P-GO. The main carbon-based photoreduction product of CdS/A-GO is CH3OH, whereas that of CdS/GO and CdS/P-GO is CO. The more conductive and hydrophilic A-GO triggers a more efficient electron transfer, CO2 adsorption, and production of hydrogen atoms from H2O dissociation, thus leading to the higher photoreduction efficiency and product change on CdS/A-GO. Besides, the COOH groups of the aspartic acid modified anhydride supply their hydrogen atoms to promote the conversion from CO2 to CH3OH on CdS/A-GO. Therefore, noncovalently functionalizing GO with different active species can efficiently improve the catalytic performance of GO. This opens a new way to design and construct noble-metal-free catalysts with enhanced activity and selectivity.

Pulsed axial epitaxy of colloidal quantum dots in nanowires enables facet-selective passivation.

Epitaxially stacking colloidal quantum dots in nanowires offers a route to selective passivation of defective facets while simultaneously enabling charge transfer to molecular adsorbates - features that must be combined to achieve high-efficiency photocatalysts. This requires dynamical switching of precursors to grow, alternatingly, the quantum dots and nanowires - something not readily implemented in conventional flask-based solution chemistry. Here we report pulsed axial epitaxy, a growth mode that enables the stacking of multiple CdS quantum dots in ZnS nanowires. The approach relies on the energy difference of incorporating these semiconductor atoms into the host catalyst, which determines the nucleation sequence at the catalyst-nanowire interface. This flexible synthetic strategy allows precise modulation of quantum dot size, number, spacing, and crystal phase. The facet-selective passivation of quantum dots in nanowires opens a pathway to photocatalyst engineering: we report photocatalysts that exhibit an order-of-magnitude higher photocatalytic hydrogen evolution rates than do plain CdS quantum dots.

Selective CO Evolution from Photoreduction of CO2 on a Metal-Carbide-Based Composite Catalyst.

A selective CO evolution from photoreduction of CO2 in water was achieved on a noble-metal-free, carbide-based composite catalyst, as demonstrated by a CO selectivity of 98.3% among all carbon-containing products and a CO evolution rate of 29.2 µmol h-1, showing superiority to noble-metal-based catalyst. A rapid separation of the photogenerated electron-hole pairs and improved CO2 adsorption on the surface of the carbide component are responsible for the excellent performance of the catalyst. The high CO selectivity is accompanied by a predominant H2 evolution, which is believed to provide a proton-deficient environment around the catalyst to favor the formation of hydrogen-deficient carbon products. The present work provides general insights into the design of a catalyst with a high product selectivity and also the carbon evolution chemistry during a photocatalytic reaction.

Photocatalytic CO2 Reduction by Carbon-Coated Indium-Oxide Nanobelts.

Indium-oxide (In2O3) nanobelts coated by a 5-nm-thick carbon layer provide an enhanced photocatalytic reduction of CO2 to CO and CH4, yielding CO and CH4 evolution rates of 126.6 and 27.9 µmol h-1, respectively, with water as reductant and Pt as co-catalyst. The carbon coat promotes the absorption of visible light, improves the separation of photoinduced electron-hole pairs, increases the chemisorption of CO2, makes more protons from water splitting participate in CO2 reduction, and thereby facilitates the photocatalytic reduction of CO2 to CO and CH4.

Immobilization of Highly Dispersed Ag Nanoparticles on Carbon Nanotubes Using Electron-Assisted Reduction for Antibacterial Performance.

Silver nanoparticles (Ag NPs) supported on certain materials have been widely used as disinfectants. Yet, to date, the antibacterial activity of the supported Ag NPs is still far below optimum. This is mainly associated with the easy aggregation of Ag NPs on the supporting materials. Herein, an electron-assisted reduction (EAR) method, which is operated at temperatures as low as room temperature and without using any reduction reagent, was employed for immobilizing highly dispersed Ag NPs on aminated-CNTs (Ag/A-CNTs). The average Ag NPs size on the EAR-prepared Ag/A-CNTs is only 3.8 nm, which is much smaller than that on the Ag/A-CNTs fabricated from the traditional thermal calcination (25.5 nm). Compared with Ag/A-CNTs fabricated from traditional thermal calcination, EAR-prepared Ag/A-CNTs shows a much better antibacterial activity to E. coli/S. aureus and antifouling performance to P. subcordiformis/T. lepidoptera. This is mainly originated from the significantly enhanced Ag(+) ion releasing rate and highly dispersed Ag NPs with small size on the EAR-prepared Ag/A-CNTs. The findings from the present work are helpful for fabricating supported Ag NPs with small size and high dispersion for efficient antibacterial process.

Peptide Self-Assembled Biofilm with Unique Electron Transfer Flexibility for Highly Efficient Visible-Light-Driven Photocatalysis.

Inspired by natural photosynthesis, biomaterial-based catalysts are being confirmed to be excellent for visible-light-driven photocatalysis, but are far less well explored. Herein, an ultrathin and uniform biofilm fabricated from cold-plasma-assisted peptide self-assembly was employed to support Eosin Y (EY) and Pt nanoparticles to form an EY/Pt/Film catalyst for photocatalytic water splitting to H2 and photocatalytic CO2 reduction with water to CO, under irradiation of visible light. The H2 evolution rate on EY/Pt/Film is 62.1 µmol h(-1), which is about 5 times higher than that on Pt/EY and 1.5 times higher than that on the EY/Pt/TiO2 catalyst. EY/Pt/Film exhibits an enhanced CO evolution rate (19.4 µmol h(-1)), as compared with Pt/EY (2.8 µmol h(-1)) and EY/Pt/TiO2 (6.1 µmol h(-1)). The outstanding activity of EY/Pt/Film results from the unique flexibility of the biofilm for an efficient transfer of the photoinduced electrons. The present work is helpful for designing efficient biomaterial-based catalysts for visible-light-driven photocatalysis and for imitating natural photosynthesis.

A simple approach to the synthesis of Cu1.8S dendrites with thiamine hydrochloride as a sulfur source and structure-directing agent.

A facile, green and environmental-friendly method for preparing Cu1.8S dendrites was developed. Copper nitrate and thiamine hydrochloride were selected as the starting materials in the water phase under hydrothermal conditions. No addition of a surfactant or a complex reagent was required for the synthesis of the Cu1.8S dendrite structures. Thiamine hydrochloride was employed as a sulfur source and structure-directing agent. The growth mechanism of Cu1.8S is tentatively discussed based on the experimental and computational results.

Cadmium sulfide quantum dots supported on gallium and indium oxide for visible-light-driven hydrogen evolution from water.

In this work, CdS quantum dots (QDs) supported on Ga2O3 and In2O3 are applied for visible-light-driven H2 evolution from aqueous solutions that contain lactic acid. With Pt as the cocatalyst, the H2 evolution rates on CdS/Pt/Ga2O3 and CdS/Pt/In2O3 are as high as 995.8 and 1032.2 µmol h(-1), respectively, under visible light (λ>420 nm) with apparent quantum efficiencies of 43.6 and 45.3% obtained at 460 nm, respectively. These are much higher than those on Pt/CdS (108.09 µmol h(-1)), Pt/Ga2O3 (0.12 µmol h(-1)), and Pt/In2O3 (0.05 µmol h(-1)). The photocatalysts have been characterized thoroughly and their band structures and photocurrent responses have been measured. The band alignment between the CdS QDs and In2O3 can lead to interfacial charge separation, which cannot occur between the CdS QDs and Ga2O3. Among the various possible factors that contribute to the high H2 evolution rates on CdS/Pt/oxide, the surface properties of the metal oxides play important roles, which include (i) the anchoring of CdS QDs and Pt nanoparticles for favorable interactions and (ii) the efficient trapping of photogenerated electrons from the CdS QDs because of surface defects (such as oxygen defects) based on photoluminescence and photocurrent studies.

2D-oriented self-assembly of peptides induced by hydrated electrons.

Peptide assembly: a 2D peptide (Aß16-22) film was produced successfully by introducing hydrated electrons into the assembly process of Aß16-22. The interplay between experiment and theoretical calculation indicates that the film formation can be enhanced through the interactions between hydrated electrons and Aß16-22.

[The clinical study of high-frequency ultrasound-guided vacuum-assisted biopsy for breast microcalcifications].

OBJECTIVE: To evaluate the clinical application of high-frequency ultrasound-guided vacuum-assisted biopsy for breast microcalcifications. METHODS: Sixty-six patients with 70 lesions of microcalcifications detected at mammography underwent high-frequency ultrasound-guided vacuum-assisted biopsy from July 2009 to October 2010. All patients were female, aged 24 to 61 years (median age 40 years). Among 70 lesions of microcalcifications, unilateral lesions were 62 cases and bilateral lesions were 4 cases. The clinical factors that affected the success of biopsy were investigated by χ(2) test and Logistic regression analysis. RESULTS: Among 70 lesions of microcalcifications, the successful rate of biopsy was 72.9% (51/70). The biopsy successful rate of microcalcifications without and with masses were 65.2% (30/46) and 87.5% (21/34) respectively (χ(2) = 3.960, P = 0.047). The biopsy successful rate of microcalcifications of maximal diameter more than 5 mm was higher than that of maximal diameter less than 5 mm (88.9% vs. 55.9%, χ(2) = 9.633, P = 0.002). The Logistic regression analysis showed that the types and maximal diameter of microcalcifications were the main factors that affected the success of biopsy. CONCLUSION: The clinical application of high-frequency ultrasound-guided vacuum-assisted biopsy was an effective option for the diagnosis of breast microcalcifications, especially for the type of microcalcifications with masses and the maximal diameter more than 5 mm.

Effects of hydration and oxygen vacancy on CO2 adsorption and activation on beta-Ga2O3(100).

The effects of hydration and oxygen vacancy on CO(2) adsorption on the beta-Ga(2)O(3)(100) surface have been studied using density functional theory slab calculations. Adsorbed CO(2) is activated on the dry perfect beta-Ga(2)O(3)(100) surface, resulting in a carbonate species. This adsorption is slightly endothermic, with an adsorption energy of 0.07 eV. Water is preferably adsorbed molecularly on the dry perfect beta-Ga(2)O(3)(100) surface with an adsorption energy of -0.56 eV, producing a hydrated perfect beta-Ga(2)O(3)(100) surface. Adsorption of CO(2) on the hydrated surface as a carbonate species is also endothermic, with an adsorption energy of 0.14 eV, indicating a slightly repulsive interaction when H(2)O and CO(2) are coadsorbed. The carbonate species on the hydrated perfect surface can be protonated by the coadsorbed H(2)O to a bicarbonate species, making the CO(2) adsorption exothermic, with an adsorption energy of -0.13 eV. The effect of defects on CO(2) adsorption and activation has been examined by creating an oxygen vacancy on the dry beta-Ga(2)O(3)(100) surface. The formation of an oxygen vacancy is endothermic, by 0.34 eV, with respect to a free O(2) molecule in the gas phase. Presence of the oxygen vacancy promoted the adsorption and activation of CO(2). In the most stable CO(2) adsorption configuration on the dry defective beta-Ga(2)O(3)(100) surface with an oxygen vacancy, one of the oxygen atoms of the adsorbed CO(2) occupies the oxygen vacancy site, and the CO(2) adsorption energy is -0.31 eV. Water favors dissociative adsorption at the oxygen vacancy site on the defective surface. This process is spontaneous, with a reaction energy of -0.62 eV. These results indicate that, when water and CO(2) are present in the adsorption system simultaneously, water will compete with CO(2) for the oxygen vacancy sites and impact CO(2) adsorption and conversion negatively.