双吡啶盐(PQ^(++))与异丙醇的光化还原反应研究

本文用自由基捕捉技术与ESR相结合的方法对五种PQ^(++)—异丙醇体系的光激发均相电子转移过程的研究结果表明PQ^(++)可被异丙醇自由基单电子还原生成PQ^+·自由基,如体系中有二苯酮存在,则电子转移反应速率大大增加.

Recent progress in production and usage of hydrogen peroxide

Hydrogen peroxide has attracted increasing interest as an environmentally benign and green oxidant that can also be used as a solar fuel in fuel cells.This review focuses on recent progress in production of hydrogen peroxide by solar-light-driven oxidation of water by dioxygen and its usage as a green oxidant and fuel.The photocatalytic production of hydrogen peroxide is made possible by combining the e^(-)and 4e-oxidation of water with the e^(-)reduction of dioxygen using solar energy.The catalytic control of the selectivity of the e^(-)vs.4e-oxidation of water is discussed together with the selectivity of the e^(-)vs.4e-reduction of dioxygen.The combination of the photocatalytic e^(-)oxidation of water and the e^(-)reduction of dioxygen provides the best efficiency because both processes afford hydrogen peroxide.The solar-light-driven hydrogen peroxide production by oxidation of water and by reduction of dioxygen is combined with the catalytic oxidation of substrates with hydrogen peroxides,in which dioxygen is used as the greenest oxidant.

Hexanuclear ring cobalt complex for photochemical CO_(2) to CO conversion

Photosynthesis in nature has been deemed as the most significant biochemical reaction,which maintains a relatively stable content of O_(2) and CO_(2) in the atmosphere.Herein,for a deeper comprehension of natural photosynthesis,an artificial photosynthesis model reaction of photochemical CO_(2) to CO conversion(CO_(2)+2 H^(+)+2e^(-)→CO+H_(2)O)catalyzed by a homogeneous hexanuclear ring cobalt complex{K_(2)[CoO_(3)PCH_(2)N(CH_(2)CO_(2))_(2)]}_(6)(Co6 complex)is developed.Using the[Ru(bpy)_(3)]^(2+)as a photosensitizer and TEOA as a sacrificial electron donor,an optimal turnover frequency of 503.3 h^(‒1) and an apparent quantum efficiency of 0.81%are obtained.The good photocatalytic CO_(2) reduction performance is attributed to the efficient electron transfer between Co6 complex and[Ru(bpy)_(3)]^(2+),which boosts the photogenerated carriers separation of the photosensitizer.It is confirmed by the j‐V curves,light‐assisted UV‐vis curves,steady‐state photoluminescence spectra and real‐time laser flash photolysis experiments.In addition,the proposed catalytic mechanism for CO_(2) reduction reaction catalyzed by the Co6 complex is explored by the potassium thiocyanate poison experiment,Pourbaix diagram and density functional theory calculations.

One-pot synthesis of mesosilica/nano covalent organic polymer composites and their synergistic effect in photocatalysis

Organic-inorganic hybrid materials provide a desirable platform for the development of novel functional materials.Here,we report the one-pot synthesis of mesoporous hybrid nanospheres by the in-situ sol-gel condensation of tetraethoxysilane around surfactant micelle-confined nano covalent organic polymer(nanoCOP)colloids.The hybrid nanospheres containing nanoCOPs uniformly distributed in the mesosilica network,inherited the visible light responsive properties of the nanoCOPs.The turnover frequency of the hybrid nanospheres is almost 12 times that of its corresponding bulk COP counterpart for the photocatalytic reductive dehalogenation of a-bromoacetophenone,which is attributed to activation of the Hantzsch ester reductant by the hydroxyl group.The existence of a volcano relationship between the activity and nano COP/mesosilica ratio confirmed the synergistic effect between nano COP and mesosilica.Our preliminary results suggest that hybridization of semiconductors and reactant-activating materials is an efficient strategy for enhancing the activity of a catalyst for photocatalysis.

Synthesis, characterization and electrochemical recognition of metal ions of three new ferrocenyl derivatives containing pyridyl moiety

Three new ferrocene （Fc） based receptors with pyridyl moiety, named methyl-6- ferrocenoylacetyl-2-pyridine carboxylate （FcLl）, 1,1＇-（2,6-bispyridyl）bis-3-ferrocenyl-l,3-propanedione （FcL2）, ferrocenecarboxaldehyde-2,6-dipicolinoyhydrazone （FcL3） were synthesized, and further characterized by elemental analysis, IR spectra, UV-Vis spectra, 1H and 13C NMR. The electrochemical properties and ion sensing properties of FcL1, FcL2 and FcL3 were also investigated by means of cyclic voltammetry in ethanol solution with 0.1 mol/L LiC104 as the supporting electrolyte. The E~ values of the receptors increase with the scanning rate increasing at high scanning rate, and Ipa/Ipo approaches unity, indicating that the redox reaction is basically reversible. Their recognition performances to different metal cations such as Cd（II）, Co（II）, Cu（II）, Hg（II）, Mn（II）, Ni（II）, Zn（II） show that the FcL1 is responsive to Cu（II） with the maximum electrochemical shift of the FcL1 for Cu（II）of about 72.0 mV, whereas the FcL2 is responsive to Cu（II） and Mn（II） with shift of 102 mV and 109 mV, respectively, and the FcL3 is responsive to Hg（II） and Mn（II） with the shift of 53.0 mV and 54.0 mV, respectively. All the results show that these receptors may have potential applications in electrochemical sensor technology, material science, and molecular devices.

Nanostructured CdS for efficient photocatalytic H2 evolution: A review

Cadmium sulfide(Cd S)-based photocatalysts have attracted extensive attention owing to their strong visible light absorption,suitable band energy levels,and excellent electronic charge transportation properties.This review focuses on the recent progress related to the design,modification,and construction of Cd S-based photocatalysts with excellent photocatalytic H2 evolution performances.First,the basic concepts and mechanisms of photocatalytic H2 evolution are briefly introduced.Thereafter,the fundamental properties,important advancements,and bottlenecks of Cd S in photocatalytic H2 generation are presented in detail to provide an overview of the potential of this material.Subsequently,various modification strategies adopted for Cd S-based photocatalysts to yield solar H2 are discussed,among which the effective approaches aim at generating more charge carriers,promoting efficient charge separation,boosting interfacial charge transfer,accelerating charge utilization,and suppressing charge-induced self-photocorrosion.The critical factors governing the performance of the photocatalyst and the feasibility of each modification strategy toward shaping future research directions are comprehensively discussed with examples.Finally,the prospects and challenges encountered in developing nanostructured Cd S and Cd S-based nanocomposites in photocatalytic H2 evolution are presented.

Photophysical and photochemical processes of riboflavin (vitamin B_2) by means of the transient absorption spectra in aqueous solution

Using time-resolved techniques of 337 and 248 nm laser flash photolysis, the photo physical and photochemical processes of riboflavin (RF, vitamin B2) were studied in detail in aqueous solution. The excited triplet state of riboflavin (3RF*) was produced with 337 nm laser, while under 248 nm irradiation, both3RF* and hydrated electron (eaq) formed from photoionization could be detected. Photobiological implications have been inferred on the basis of reactivity of3RF* including energy transfer, electron transfer and hydrogen abstraction. The RF·+ was generated by oxidation of SO4 ·-radical with the aim of confirming the results of photolysis.

Redox-triggered hydroarylation of o-(hydroxyalkyl)arylalkynes with arylsulfonyl chlorides using visible light catalysis

A new radical-mediated method for the synthesis of 1-(2-(1,2-diarylvinyl)phenyl)ethan-1-ones by the redox hydroarylation of o-(hydroxyalkyl)arylalkynes with arylsulfonyl chlorides is described. This visible light catalysis method proceeds via a sequence of the radical addition of aryl group across the C?C triple bond, protonation and redox reaction, and represents a new redox transformation reaction directed by a neighboring hydroxyl group.

Controllable synthesis of titania/reduced graphite oxide nanocomposites with various titania phase compositions and their photocatalytic performance

A facile method is presented for preparing TiO2/reduced graphite oxide （RGO） nanocomposites with phase-controlled TiO2 nanoparticles via redox reaction between the reductive titanium （III） precursor and graphite oxide （GO）, and a series of TiO2/RGO composites with various TiO2 phase compositions were obtained. In all the titania/RGO composites, the TiO2 nanoparticles were uniformly distributed on the surface of the RGO. The TiO2 consisted of anatase phase particles in the form of square-plates with edges less than 10 nm and the rutile phase nanorods in diameters less than 10 nm. The performances of the as-prepared TiO2/RGO composites were investigated on catalytically degrading phenol under visible light irradiation. The TiO2/RGO composites can effectively degrade phenol under visible light irradiation, and the phase composition of TiO2 in the composites significantly influences the activities of these catalysts.