Field Measurement of NO2 and RNO2 by Two-Channel Thermal Dissociation Cavity Ring Down Spectrometer

A two-channel thermal dissociation cavity ring down spectroscopy （CRDS） instrument has been built for in situ, real-time measurement of NO2 and total RNO2 （peroxy nitrates and alkyl nitrates） in ambient air, with a NO2 detection limit of 0.10 ppbv at 1 s. A 6-day long measurement was conducted at urban site of Hefei by using the CRDS instrument with a time resolution of 3 s. A commercial molybdenum converted chemiluminescence （Mo-CL） instrument was also used for comparison. The average RNO2 concentration in the 6 days was measured to be 1.94 ppbv. The Mo-CL instrument overestimated the NO2 concentration by a bias of ＋1.69 ppbv in average, for the reason that it cannot distinguish RNO2 from NO2. The relative bias could be over 100% during the afternoon hours when NO2 was low but RNO2 was high.

Photoelectrocatalysis for high‐value‐added chemicals production

Photoelectrocatalysis(PEC)is a promising approach that can convert renewable solar energy into chemical energy,while most concern is concentrated on PEC water splitting to obtain high‐value‐added fuel—hydrogen.In practice,more economic benefits can be produced based on PEC technique,such as H_(2)O oxidative H_(2)O_(2) synthesis,organic selective oxidation,organic pollutants degradation and CO_(2) reduction.Although there are plenty of excellent reviews focusing on the PEC water splitting system,the production of various high‐value‐added chemicals in PEC systems has not been discussed synthetically.This Account will focus on the production process of various high‐value‐added chemicals through PEC technology.The photoelectrode design,reaction environment and working mechanisms of PEC systems are also discussed in detail.We believe that this comprehensive Account of the expanded application of photoelectrocatalysis can add an inestimable impetus to the follow‐up development of this technology.

Iron Arene Salts as Initiators for Thermal Curing of Epoxides by Photo-catalysis

[Cyclopentadien-Fe-naphthalene]BF4(CFN) and [cyclopentadien-Fe-anisole]BF4(CFA) as thermal cationic initiators for the curing of epoxide E44 and GGE were investigated. CFN brought out the curing of E44 at 89.1℃ and that of GGE at 148.7℃. However, CFA had much less thermal initiating activity under 300℃. Under UV radiation for short time, the thermal initiating activities of CFN and CFA were enhanced obviously. It was observed that the initiating onset temperature decreased and the evolved heat of the curing increased. Both CFN and CFA can carry out the polymerization of E44 and GGE near 85℃ and 112℃ by UV radiation.

The Role of the Dipole Interaction of Molecules with Charged Particles in the Polar Stratosphere

Our analysis of published results of experiments in the Polar Regions substantiates and further develops our new approach to the photochemical processes in the polar stratosphere involving the charged particles. The dipole interaction of molecules with charged particles, primarily with ions, leads to the adhesion and disintegration of a number of molecules including ozone. Molecules acquire additional energy on the surface of the charged particles, enabling reactions that are not possible in space. Galactic cosmic rays are the main source of ions in the polar stratosphere, their equilibrium concentration at altitudes of 15 to 25 km can reach up ~ （1-5） ~ 103 ions/cm3. Estimations show that if the ozone destruction in the regime of＂collision＂ with ions then the lifetime of ozone will vary from 10 days to 2 months. We suppose that alongside with the chlorine mechanism of ozone destruction there is a mechanism of ozone decay on a charged particle which can act also at those latitudes and altitudes where chlorine oxide CIO is absent, as well as in the night conditions. Here, we demonstrated the close connection of photochemical processes with the dynamic, electrical and condensational phenomena in the stratosphere, in particular, with the accumulation of unipolar charged particles on the upper and lower boundaries of the polar stratospheric clouds and aerosol layers as a result of the activity of the global electric circuit.

Synthesis of butterfly-like BiVO4/RGO nanocomposites and their photocatalytic activities

A simple and high efficient method was proposed for the synthesis of uniform three dimensional （3D） BiVO4/reduced graphene oxide （RGO） nanocomposite photocatalyst by adopting the microwave assistant and using Bi （NO3）3·5H2O, graphene oxide （GO） and NH4VO3 as precursor. The as-obtained composites were well characterized with the aid of various techniques to study the morphology, structure, composition, optimal and electrical property. In the as-obtained composites, the GO sheets were fully reduced into RGO, and monoclinic structure BiVO4 crystallized completely into butterfly-like BiVO4 lamellas and well bonded with the RGO lamellas. The length and the width of the butterfly-like BiVO4 particle were about 1.5 μm, and the thickness of the flake was about 20 nm. Photocatalytic performances of BiVO4/RGO composite and pure BiVO4 particle have been evaluated by investigating the reduction of Cr（VI） ion-contained wastewater under simulated solar light irradiation, where the BiVO4/RGO composite displayed enhanced photocatalytic activity. It is found that the pseudo-first-order rate constants （k） for the photocatalytic reduction of Cr （VI） by BiVO4/RGO composite was about 4 times as high as that of the pure BiVO4. The present work suggested that the combination of BiVO4 and RGO displayed a remarkable synergistic effect, which led to enhanced photo-catalytic activity on Cr（VI） reduction.

Protection strategy for improved catalytic stability of silicon photoanodes for water oxidation

Silicon-based electrodes have attracted great attention in the artificial photosynthetic systems that mimic natural photosynthesis and directly convert the solar energy into chemical energy. Despite significant efforts to date,catalytic stability of the silicon photoelectrodes is limited by their poor electrochemical stability. The formation of passivation or protective layers provides a feasible strategy to improve the photocatalytic stability of silicon photoelectrodes. Many candidates including metals, metal oxides, metal silicides and polymers have been explored as the protection layers for silicon photoelectrodes. The present review gives a concise overview of the protected silicon photoanodes for water oxidation with a focus on the relationship between the structural architecture of silicon photoanodes and their photocatalytic activity and stability.

The intensification of luminol electrochemiluminescence by metallic oxide nanoparticles

In this work, the intensification of luminol electrochemiluminescence (ECL) by metallic oxide nanoparticles (MONPs), as ZnO, MnO2,In2O3 and TiO2 , under alkaline condition is reported and the related mechanism is studied. It is found that all four types of those MONPs exhibit the effect toward the ECL intensification of luminol. Furthermore, the silica sol-gel film is taken to immobilize the MONPs onto the platinum electrodes. The so-obtained modified electrodes also show the enhanced ECL and better signal/noise ratio, as well improved signal stability. Finally, the ECL reagent, luminol, is immobilized together with the MONPs onto the electrode surface to perform as the ECL sensor. On resulting sensors, good linear responses are obtained toward hydrogen peroxide. The mechanism of intensification of luminol ECL by MONPs is discussed in this paper. It is proposed that the ECL intensification can be attributed to the production of reactive oxygen species, as well as the adsorption of luminol on surface of MONPs.