Defects on CoS2-x : Tuning Redox Reactions for Sustainable Degradation of Organic Pollutants.

It is important to develop self-producing reactive oxygen species (ROSs) systems and maintain the continuous and effective degradation of organic pollutants. Herein, for the first time, a system of ultrasound-treated CoS2-x mixed with Fe2+ is constructed to sustainably release singlet oxygen (1 O2 ) for the effective degradation of various organic pollutants, including dyes, phenols, and antibiotics. Ultrasonic treatment produces defects on the surface of CoS2 which promote the production of ROSs and the circulation of Fe3+ /Fe2+ . With the help of Co4+ /Co3+ exposed on the surface of CoS2-x , the directional conversion of superoxide radical (. O2- ) to 1 O2 is realized. The CoS2-x /Fe2+ system can degrade organic pollutants efficiently for up to 30 days, which is significantly better than the currently recognized CuPx system (<3 days). Therefore, CoS2-x provides a new choice for the long-term remediation of organic pollutants in controlling large area river pollution.

Non-oxidative Coupling of Methane: N-type Doping of Niobium Single Atoms in TiO2 -SiO2 Induces Electron Localization.

Photodriven nonoxidative coupling of CH4 (NOCM) is an attractive potential way to use abundant methane resources. Herein, an n-type doped photocatalyst for NOCM is created by doping single-atom Nb into hierarchical porous TiO2 -SiO2 (TS) microarray, which exhibits a high conversion rate of 3.57 µmol g-1 h-1 with good recyclability. The Nb dopant replaces the 6-coordinated titanium on the (1 0 1) plane and forms shallow electron-trapped surface polarons along [0 1 0] direction and the comparison of different models proves that the electron localization caused by the n-type doping is beneficial to both methane activation and ethane desorption. The positive effect of n-type dopant on CH4 conversion is further verified on Mo-, W- and Ta-doped composites. In contrast, the doping of p-type dopant (Ga, Cu, Fe) shows a less active influence.

Designing 3D-MoS2 Sponge as Excellent Cocatalysts in Advanced Oxidation Processes for Pollutant Control.

3D-MoS2 can adsorb organic molecules and provide multidimensional electron transport pathways, implying a potential application for environment remediation. Here, we study the degradation of aromatic organics in advanced oxidation processes (AOPs) by a 3D-MoS2 sponge loaded with MoS2 nanospheres and graphene oxide (GO). Exposed Mo4+ active sites on 3D-MoS2 can significantly improve the concentration and stability of Fe2+ in AOPs and keep the Fe3+ /Fe2+ in a stable dynamic cycle, thus effectively promoting the activation of H2 O2 /peroxymonosulfate (PMS). The degradation rate of organic pollutants in the 3D-MoS2 system is about 50 times higher than without cocatalyst. After a 140 L pilot-scale experiment, it still maintains high efficiency and stable AOPs activity. After 16 days of continuous reaction, the 3D-MoS2 achieves a degradation rate of 120 mg L-1 antibiotic wastewater up to 97.87 %. The operating cost of treating a ton of wastewater is only US$ 0.33, suggesting huge industrial applications.

Recent advances in visible-light-responsive photocatalysts for hydrogen production and solar energy conversion--from semiconducting TiO2 to MOF/PCP photocatalysts.

The present perspective describes recent advances in visible-light-responsive photocatalysts intended to develop novel and efficient solar energy conversion technologies, including water splitting and photofuel cells. Water splitting is recognized as one of the most promising techniques to convert solar energy as a clean and abundant energy resource into chemical energy in the form of hydrogen. In recent years, increasing concern is directed to not only the development of new photocatalytic materials but also the importance of technologies to produce hydrogen and oxygen separately. Photofuel cells can convert solar energy into electrical energy by decomposing bio-related compounds and livestock waste as fuels. The advances of photocatalysts enabling these solar energy conversion technologies have been going on since the discovery of semiconducting titanium dioxide materials and have extended to organic-inorganic hybrid materials, such as metal-organic frameworks and porous coordination polymers (MOF/PCP).

Hydration of LiOH and LiCl-Near-Infrared Spectroscopic Analysis.

The hydration behavior of LiOH, LiOH·H2O, and LiCl was observed by near-infrared (NIR) spectroscopy. Anhydrous LiOH showed two absorption bands at 7340 and 7171 cm-1. These NIR bands were assigned to the first overtone of surface hydroxyls and interlayer hydroxyls of LiOH, respectively. LiOH·H2O showed two absorption bands at 7137 and 6970 cm-1. These NIR bands were assigned to the first overtone of interlayer hydroxyls and H2O molecules coordinated with Li+, respectively. The interlayer OH- and the coordinated H2O of LiOH·H2O were not modified even when the LiOH·H2O was exposed to air. In contrast, anhydrous LiOH was slowly hydrated for several hours, to form LiOH·H2O under ambient conditions (RH 60%). Kinetic analysis showed that the hydration of the interlayer OH- of LiOH proceeded as a second-order reaction, indicating the formation of intermediate species-[Li(H2O) x (OH)4]3- (x = 1 or 2). However, the hydration of the LiOH surface did not follow a second-order reaction because the chemisorption of H2O molecules onto the defect sites of the LiOH surface does not need to crossover the energy barrier. Furthermore, we succeeded in observing the hydration of deliquescent LiCl, including the formation of LiCl solution for several minutes by NIR spectroscopy.

Incorporation of arene metal carbonyl complexes within inorganic-organic hybrid mesoporous materials by CVD method.

Simple chemical vapor deposition (CVD) of M(CO), (M = Cr, Mo, W) onto phenylene- and biphenylene-bridged organosilica mesoporous materials (HMM-ph, HMM-biph) led to the efficient formation of C6H4M(CO)3 and (C6H4)2M(CO)3 complexes, respectively, which are directly fixed and incorporated within the framework structure of HMM-ph and HMM-biph having molecular-scale periodicity in the pore walls. FT-IR investigations revealed that thus formed C6H4M(CO), or (C6H4)2M(CO)3 complexes are thermally stable even under thermovacuum treatment at 473 K.

Bimetallic MOF-templated synthesis of alloy nanoparticle-embedded porous carbons for oxygen evolution and reduction reactions.

Pyrolysis of metal-organic frameworks (MOFs) to produce metal nanoparticles embedded inside a porous carbon matrix (M@PC) has drawn a lot of attention in recent years. Notably, Fe nanoparticles trapped in a carbon matrix (Fe@PC) have been reported to efficiently promote oxygen evolution and reduction reactions (OER/ORR). However, research on the effect of doping in Fe particles has been scarce because of the difficulty in synthesizing alloys of small size at elevated temperature. Herein, we focus on the development of bimetallic MOFs composed of Fe and a second metal M (M = Cr, Ni, Co, and Mn) made from a preassembled cluster and their sacrificial use to synthesize FeM@PC composites. After optimising the pyrolysis conditions and determining the optimal structure of an MOF template, the materials were used in the electrocatalytic OER and ORR in 0.1 M KOH aqueous solution. Results showed that Co-Fe alloy composites exhibited the best activity for the OER with a 210 mV cathodic shift to achieve 10 mA cm-2 compared to that of pure Fe@PC. On the other hand, the oxygen reduction reaction most efficiently proceeded on the Mn-Fe alloy composite, showing an 80 mV anodic shift in comparison with all other doped materials.

Investigations on the effect of Mn ions on the local structure and photocatalytic activity of Cu(I)-ZSM-5 catalysts.

The introduction of Mn ions into Cu(I)-ZSM-5 was found to lead to an enhancement of the photocatalytic activity for the direct decomposition of N2O into N2 and O2 at 298 K. Various in-situ techniques such as ESR, photoluminescence, XAFS as well as a combination of CO-FT-IR and CO-TPD measurements revealed that the accommodation of Mn ions within ZSM-5 zeolite cavities significantly affects the location sites of the ion-exchanged Cu(II) ions as well as the local structure of the Cu(I) ion species formed by evacuation at high temperatures. Moreover, the introduction of Mn ions into ZSM-5 led to an increase in the amount of 3-coordinated Cu(I) species at the main channel of the zeolite, playing a major role as the active species for the photocatalytic decomposition of N2O into N2 and O2.

Preparation of nitrogen-substituted TiO2 thin film photocatalysts by the radio frequency magnetron sputtering deposition method and their photocatalytic reactivity under visible light irradiation.

Nitrogen-substituted TiO2 (N-TiO2) thin film photocatalysts have been prepared by a radio frequency magnetron sputtering (RF-MS) deposition method using a N2/Ar mixture sputtering gas. The effect of the concentration of substituted nitrogen on the characteristics of the N-TiO2 thin films was investigated by UV-vis absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy (SEM) analyses. The absorption band of the N-TiO2 thin film was found to shift smoothly to visible light regions up to 550 nm, its extent depending on the concentration of nitrogen substituted within the TiO2 lattice in a range of 2.0-16.5%. The N-TiO2 thin film photocatalyst with a nitrogen concentration of 6.0% exhibited the highest reactivity for the photocatalytic oxidation of 2-propanol diluted in water even under visible (lambda > or = 450 nm) or solar light irradiation. Moreover, N-TiO2 thin film photocatalysts prepared on conducting glass electrodes showed anodic photocurrents attributed to the photooxidation of water under visible light, its extent depending on wavelengths up to 550 nm. The absorbed photon to current conversion efficiencies reached 25.2% and 22.4% under UV (lambda = 360 nm) and visible light (lambda = 420 nm), respectively. UV-vis and photoelectrochemical investigations also confirmed that these thin films remain thermodynamically and mechanically stable even under heat treatment at 673 K. In addition, XPS and XRD studies revealed that a significantly high substitution of the lattice O atoms of the TiO2 with the N atoms plays a crucial role in the band gap narrowing of the TiO2 thin films, enabling them to absorb and operate under visible light irradiation as a highly reactive, effective photocatalyst.

Extending the photoresponse of TiO2 to the visible light region: photoelectrochemical behavior of TiO2 thin films prepared by the radio frequency magnetron sputtering deposition method.

TiO(2) thin films prepared by a radio frequency magnetron sputtering (RF-MS) deposition method were found to show an enhanced photoelectrochemical response in the visible light region. By controlling the temperature and the gaseous medium during the deposition step, it was possible to control the properties of these films. The photoelectrochemical behavior of the sputtered TiO(2) thin films was compared with that of a commercial TiO(2) sample, and the sputtered films showed higher incident photon to the charge carrier generation efficiency (IPCE of 12.6% at 350 nm) as well as power conversion efficiency (0.33% at 1.84 mW/cm(2)) than the commercial TiO(2) sample. Femtosecond transient absorption spectroscopy experiments have revealed that a major fraction of photogenerated electrons and holes recombine within a few picoseconds, thus limiting photocurrent generation efficiency. The mechanistic insights obtained in the present study should aid in designing semiconductor nanostructures that will maximize the charge separation efficiency and extend the response of the large band gap semiconductor TiO(2) into visible light regions.

Visible-light-driven photocatalytic water oxidation catalysed by iron-based metal-organic frameworks.

An iron-based metal-organic framework, MIL-101(Fe), promotes photocatalytic water oxidation to produce oxygen from aqueous silver nitrate solution under visible-light irradiation. The finely dispersed iron-oxo clusters embedded as nodes of the porous framework would contribute importantly to the efficient promotion of the reaction as compared to bulk hematite (α-Fe2O3).

Design of Zeolitic Imidazolate Framework Derived Nitrogen-Doped Nanoporous Carbons Containing Metal Species for Carbon Dioxide Fixation Reactions.

Various N-doped nanoporous carbons containing metal species were prepared by direct thermal conversion of zeolitic imidazolate frameworks (ZIFs; ZIF-7, -8, -9, and -67) at different temperatures (600, 800, and 1000 °C). These materials were utilized as bifunctional acid-base catalysts to promote the reaction of CO2 with epoxides to form cyclic carbonates under 0.6 MPa of CO2 at 80 °C. The catalyst generated by thermal conversion of ZIF-9 at 600 °C (C600-ZIF-9) was found to exhibit a higher catalytic activity than the other ZIFs, other conventional catalysts, and other metal-organic framework catalysts. The results of various characterization techniques including elemental analysis, X-ray diffraction, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and transmission electron microscopy show that C600-ZIF-9 contains partly oxidized Co nanoparticles and N species. Temperature-programmed desorption measurements by using CO2 and NH3 as probe molecules revealed that C600-ZIF-9 has both Lewis acid and Lewis base catalytic sites. Finally, the substrate scope was extended to seven other kinds of epoxides.

Highly photosensitive graphene field-effect transistor with optical memory function.

Graphene is a promising material for use in photodetectors for the ultrawide wavelength region: from ultraviolet to terahertz. Nevertheless, only the 2.3% light absorption of monolayer graphene and fast recombination time of photo-excited charge restrict its sensitivity. To enhance the photosensitivity, hybridization of photosensitive material and graphene has been widely studied, where the accumulated photo-excited charge adjacent to the graphene channel modifies the Fermi level of graphene. However, the charge accumulation process slows the response to around a few tens of seconds to minutes. In contrast, a charge accumulation at the contact would induce the efficient light-induced modification of the contact resistance, which would enhance its photosensitivity. Herein, we demonstrate a highly photosensitive graphene field-effect transistor with noise-equivalent power of ~3 × 10(-15) W/Hz(1/2) and with response time within milliseconds at room temperature, where the Au oxide on Au electrodes modulates the contact resistance because of the light-assisted relaxation of the trapped charge at the contact. Additionally, this light-induced relaxation imparts an optical memory function with retention time of ~5 s. These findings are expected to open avenues to realization of graphene photodetectors with high sensitivity toward single photon detection with optical memory function.

Visible-light, photoredox catalyzed, oxidative hydroxylation of arylboronic acids using a metal-organic framework containing tetrakis(carboxyphenyl)porphyrin groups.

A Zr-based metal-organic framework with tetrakis(carboxyphenyl)porphyrin groups (Zr-MOF-TCPP: MOF-525) has been utilized as a photoredox catalyst to promote oxidative hydroxylation of arylboronic acids under green LED light irradiation. Zr-MOF-TCPP displays a superior catalytic activity for this process over the corresponding homogeneous catalyst (H4TCPP).

Development of a Ru complex-incorporated MOF photocatalyst for hydrogen production under visible-light irradiation.

A Ru complex-incorporated Ti-based MOF (Ti-MOF-Ru(tpy)2) has been synthesised by using a bis(4'-(4-carboxyphenyl)-terpyridine)Ru(ii) complex (Ru(tpy)2) as an organic linker. Ti-MOF-Ru(tpy)2 promotes photocatalytic hydrogen production from water containing a sacrificial electron donor under visible-light irradiation up to 620 nm.

Effect of pore sizes on catalytic activities of arenetricarbonyl metal complexes constructed within Zr-based MOFs.

Arenetricarbonyl metal complexes ([-phM(CO)3-] and [-biphM(CO)3-]; ph = phenylene, biph = biphenylene, M = Mo, Cr) constructed within Zr-based MOFs act as highly active and selective catalysts for epoxidation of cyclooctene. Catalytic activities of these complexes are enhanced with increasing the pore sizes of Zr-based MOFs.

Preparation and characterization of unique inorganic-organic hybrid mesoporous materials incorporating arenetricarbonyl complexes [-C6H4M(CO)3-] (M = Cr, Mo).

Unique inorganic-organic hybrid mesoporous materials incorporating arenetricarbonyl complexes [-C6H4M(CO)3-] (M = Cr, Mo) within their mesoporous frameworks have been successfully prepared by a simple CVD treatment of the phenylene-bridged organosilica mesoporous materials with metal hexacarbonyls [M(CO)6] (M = Cr, Mo). FT-IR and UV-vis investigations revealed that the arenetricarbonyl complexes exist stably even at temperatures above 473 K under vacuum.