Recent advances in phenazine-linked porous catalysts toward photo/electrocatalytic applications and mechanism

In recent years,porous organic catalysts have been developed and become research hotspots in photo/electrocatalysis due to their inherent pores,high specific surface area,chemical and thermal stability,and diverse functional building blocks.Phenazine-linked organic catalysts,exhibited excellent conjugation,electrical conductivity,chemical,and thermal stability,could bring in N atoms with specific numbers and positions to regulate electron levels,anchor metals,and absorb near-infrared light,which expands solar energy utilization.These advantages of the phenazine-linked catalysts attracted our group and numerous researchers to conduct experimental and computational work on photo/electrocatalytic applications and mechanisms.This review summarizes the recent significant research progress,synthesis methods,photo/electrocatalytic performance,and applications of relative phenazine-linked catalysts.Furthermore,the photo/electrocatalytic mechanism was systematized and summarized by combining experiments and density functional theory calculations simultaneously.

Synthesis of Ag/AgCl/Fe-S plasmonic catalyst for bisphenol A degradation in heterogeneous photo-Fenton system under visible light irradiation

A novel plasmonic photo‐Fenton catalyst of Ag/AgCl/Fe‐S was synthesized by ion exchange and photoreduction methods.The obtained catalyst was characterized by X‐ray diffraction,X‐ray photoelectron spectroscopy,scanning electron microscope imaging,and Brunauer‐Emmett‐Teller measurements.Moreover,the photocatalytic activity of Ag/AgCl/Fe‐S was investigated for its degradation activity towards bisphenol A(BPA)as target pollutant under visible light irradiation.The effects of H2O2concentration,pH value,illumination intensity,and catalyst dosage on BPA degradation were examined.Our results indicated that the Ag/AgCl material was successfully loaded onto Fe‐sepiolite and showed a high photocatalytic activity under illumination by visible light.Furthermore,active species capture experiments were performed to explore the photocatalytic mechanism of the Ag/AgCl/Fe‐S in this heterogeneous photo‐Fenton process,where the major active species included hydroxyl radicals(?OH)and holes(h+).

Photocatalytic Synthesis of Hydrocarbon Oxygenates from C_2H_6 and CO_2 over Pd-MoO_3/SiO_2 Catalyst

Pd-MoO3/SiO2 catalyst has been prepared using the method of incipient wetness impregnation. The photo absorbing behaviors and chemisorbing properties of the catalyst have been characterized by UV-vis spectra and TPD-MS experiments. The results indicated that metal Pd loaded on MoOa/SiO2 has a significant effect on the photo absorbing performance of MoOa/SiO2, and an obvious blue shift of the absorption edge is produced. Under UV irradiation, the chemisorption state of CO2 undergoes decomposing process to form CO at 481 K, and a two-site adsorption state of ethane can be formed at around 496 K. Photo-oxidation of ethane using carbon dioxide can mainly produce propanal, ethanol and acetaldehyde in the temperature range of 353-423 K. The presence of metal Pd improves the catalytic activity remarkably.

Ca and Sr co-doping induced oxygen vacancies in 3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts for boosting low-temperature oxidative coupling of methane

It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.

Amino-Functionalized Reduced Graphene-Oxide-Copper (I) Oxide Composite: A Prospective Catalyst for Photo-Reduction of CO2

In the present article, an easy synthetic strategy of a novel composite photo-catalyst comprising of amino-functionalized reduced graphene oxide and Cu2O has been proposed. Role of this composite catalyst in photo reduction of CO2 has been analyzed and it is shown that both amino groups and reduced grapheme oxide, participate in enhancing quantum yield of the photo reduction process.

非均相Photo-Fenton反应中负载型光催化剂研究进展

与Fenton、类Fenton、UV/H2O2以及均相Photo-Fenton体系相比,非均相Photo-Fenton反应体系具有反应效率高?有效pH范围宽广以及催化剂可再生利用等优势,是一项极具发展潜力的新型高级氧化工艺。非均相Photo-Fenton反应体系的关键问题是催化剂问题。着重介绍了近几年来有关非均相Photo-Fenton体系中负载型光催化剂的研究发展概况,对目前光催化剂存在的一些问题以及未来发展方向进行了总结与展望。

Propene and CO oxidation on Pt/Ce-Zr-SO_4^(2-) diesel oxidation catalysts:Effect of sulfate on activity and stability

Platinum/cerium-zirconium-sulfate（Pt/Ce-Zr-SO_4^（2-）） catalysts were prepared by wetness impregnation.Catalytic activities were evaluated from the combustion of propene and CO.Sulfate（SO_4^（2-））addition improved the catalytic activity significantly.When using Pt/Ce-Zr-SO_4^（2-） with 10 wt%SO_4^（2-）,the temperature for 90%conversion of propene and CO decreased by 75℃ compared with Pt/Ce-Zr.The conversion exceeded 95%at 240℃ even after 0.02%sulfur dioxide poisoning for 20 h.Temperature-programmed desorption of CO and X-ray photoelectron spectroscopy analyses revealed an improvement in Pt dispersion onto the Ce-Zr-SO_4^（2-） support,and the increased number of Pt particles built up more Pt^（-）-（SO_4^（2-））^（-） couples,which resulted in excellent activity.The increased total acidity and new Bronsted acid sites on the surface provided the Pt/Ce-Zr-SO_4^（2-） with good sulfur resistance.

非均相Photo-Fenton反应中催化剂及其光催化机理研究进展

非均相Photo-Fenton反应体系具有反应效率高、有效pH范围宽广以及催化剂可再生利用等优势,是一项极具发展潜力的新型高级氧化工艺。本文简单介绍了近几年来有关非均相Photo-Fenton体系中负载型光催化剂的最新研究成果,主要包括以SiO_2、Al_2O_3、分子筛、碳基材料、黏土材料等无机载体,以及以离子交换树脂和有机纤维材料等有机载体制备的负载型光催化剂,并且在此基础上着重讨论了光催化机理。对目前非均相Photo-Fenton反应存在的一些问题以及未来发展方向作了总结与展望。

Solar-Driven Hydrogen Peroxide Production Using Polymer-Supported Carbon Dots as Heterogeneous Catalyst

Safe, sustainable, and green production of hydro gen peroxide is an exciting proposition due to the role of hydrogen peroxide as a green oxidant and energy carrier for fuel cells. The current work reports the development of carbon dot-impregnated waterborne hyperbranched polyurethane as a heterogeneous photo-catalyst for solar-driven production of hydrogen peroxide. The results reveal that the carbon dots possess a suitable band-gap of 2.98 eV,which facilitates effective splitting of both water and ethanol under solar irradiation. Inclusion of the carbon dots within the eco-friendly polymeric material ensures their catalytic activity and also provides a facile route for easy catalyst separation, especially from a solubilizing medium.The overall process was performed in accordance with the principles of green chemistry using bio-based precursorsand aqueous medium. This work highlights the potential of carbon dots as an effective photo-catalyst.

以消化污泥和硫酸亚铁铵为原料快速制备高效稳定的Photo-Fenton反应催化剂

厌氧消化因其能将污泥中的有机物转化为沼气而备受关注。然而,经过厌氧消化后的沼渣即消化污泥仍含有高浓度的重金属和其他有害物质,给传统的污泥处理处置带来一系列的困难。该文通过一种简单的合成方法将消化污泥变成稳定高效的非均相催化剂。通过对比消化污泥+(NH4)2Fe(SO4)2和单纯消化污泥对RhB(罗丹明B)降解速率的影响,发现人为添加一定量的(NH4)2Fe(SO4)2,可以有效提高RhB的降解速率,使之在10 min后降解率达到80%,20 min内降解率达到95%,从而大大减少降解有机物所需要的时间。

Preparation,characterization and catalytic properties of S_2O_8^(2-)/ZrO_2-CeO_2 solid superacid catalyst

A novel solid superacid catalyst S2O8^2-/ZrO2-CeO2 was prepared by a coprecipitation method and characterized by means of XRD FTIR, BET, TEM and DSC/TG analysis methods. The results indicated that incorporation of appropriate amounts of Ce into the catalyst was beneficial to the formation of sole tetragonal ZrO2 and effectively prevented from the formation of monoclinic ZrO〉 and restrained the loss of sulfated species. XRD revealed the presence of tetragonal Ce0.16Zr0.84O2phase in the case of S2O8^2-/ZrO2-CeO2 calcined above 500 ℃. Catalytic activities of S2O8^2-/ZrO2-CeO2 for the esterification of lactic acid with n-butanol was studied. The results showed that the optimum conditions were as follows： calcination temperature of the catalyst 600 ℃, n（lactic acid）：n（n-butyl alcohol）=1.0：3.0, w（S2O8^2-/ZrO2- CeO2）=12.0%, reaction temperature 145 ℃, and reaction time 2 h. The esterification efficiency of lactic acid was about 96.6%.

WO_(3)-TiO_(2)负载的Pt单原子催化剂光热协同催化丙烷和丙烯氧化

单原子催化剂(single-atom catalyst,SAC)可以最大化金属原子利用率,并具有独特的电子特性,已经在各种催化反应中进行了广泛的探索。然而,与纳米催化剂相比,贵金属SAC在烃类氧化反应中通常被认为是不活泼的。在本文中,证明了WO_(3)-TiO_(2)负载的Pt SAC(Pt1/WO_(3)-TiO_(2))在光热协同催化氧化C3H8和C3H6这两种典型的挥发性有机化合物(VOCs)中表现出比相应的纳米催化剂(PtNP/WO_(3)-TiO_(2))高得多的活性。研究发现,Pt1/WO_(3)-TiO_(2)和PtNP/WO_(3)-TiO_(2)都可以通过克服氧中毒来提高光热协同催化C3H8氧化的活性。值得注意的是,Pt1/WO_(3)-TiO_(2)的反应速率达到了3792μmol∙gPt−1∙s^(−1),这对C3H8氧化是一个新的突破。更有趣的是,由于C3H6在PtNP/WO_(3)-TiO_(2)上的强吸附导致催化剂C3H6中毒,因此PtNP/WO_(3)-TiO_(2)上的光热协同催化C3H6氧化无法进行。但是,得益于C3H6和Pt单原子之间适中的相互作用,Pt1/WO_(3)-TiO_(2)上的C3H6中毒在光照下可以被克服。因此,Pt1/WO_(3)-TiO_(2)在光热协同催化C3H6氧化中显示出更高的活性。这项工作表明,SAC的优势不仅在于节约贵金属,还在于可以根据其独特的电子特性发现新的催化反应。

LaSrNiO_(4-λ) with K_2NiF_4 Strcture──A Highly Active Catalyst for Direct Decomposition of Nitrogen Monoxide

A series of perovskite-like mixed oxides La2-xSrxMO4±λ(M =Cu, Co,Ni; x=0,1 ) was prepared and characterized using X-ray powder diffraction. The catalytic properties of these catalysts in NO decompositiori were tested. The results showed that LaSrNiO4-λ with K2NiF4 structure is very active and stable for the decomposition of NO.

Conjugated polymerized bimetallic phthalocyanine based electrocatalyst with Fe-N_(4)/Co-N_(4) dual-sites synergistic effect for zinc-air battery

The bifunctional oxygen catalyst is essential for zinc-air batteries(ZABs).Here,an efficient bifunctional oxygen catalyst,PPcFeCo/3D-G,is obtained throughπ-πinteraction between the conjugated polymerized iron-cobalt phthalocyanine(PPcFeCo)with excellent thermal stability and three-dimensional graphene(3D-G).The bimetallic synergistic effect of PPcFeCo,verified by DFT(Density functional theory)calculation,andπ-πinteractions enhances the catalytic activity and durability of the PPcFeCo/3D-G.Regarding electrochemical performance,the PPcFeCo/3D-G with a high electron transfer number(3.98,@0.768 V vs.RHE)has excellent half-wave potential(E_(1/2)=0.890 V vs.RHE)and exhibits outstanding reversibility(ΔE=0.700 V,ΔE=Ej=10-E_(1/2)).The liquid ZAB(LZAB)employed PPcFeCo/3D-G displays a high power density(222 m W cm^(-2)),a specific capacity(792 m A h g-1),and excellent durability(120 h).This work has guiding significance for the preparation of high-efficiency bifunctional catalysts.

The Microwave Synthesis and Photo-catalytic Activity of SnO_2·TiO_2 Nano-composite

A microwave-assisted heating approach was developed to fabricate SnO2·TiO2 nano-composite in an aqueoas sohaion of sulphuric acid in the presence of SnO2 nano-powder and titanium sulfate. Powder X-ray diffraction （ XRD ） pattern indicates that the products were a composite with both of anatase-type TiO2 and tetrahedrul SnO2. The prnducts were also characterized by transmission electron microscolry （ TEM ）, photoluminescence （PL） spectra. The photo-catalytic property of the as-prepared sample has ulso been studied. The result indicates that the as-prepared sample is a good photo-catadyst.

Ce_xTi_(1-x)O_2 Mixed Oxides Supported CuO Catalyst for NO Reduction by CO

Ce x Ti 1- x O 2 mixed oxides of different mole ratios ( x =0, 0.1, 0.2～0.9, 1.0) were prepared by co precipitation of TiCl 4 with Ce(NO 3) 3 and then loaded with different amounts of CuO. The effects of CuO on NO+CO reaction were investigated, and the structure and reductive properties of various CuO/Ce x Ti 1- x O 2 were characterized by the methodologies of BET, TPR and XRD. The results show that different Ce/Ti mole ratios and calcination temperatures induce changes of structure and reductive properties of the Ce x Ti 1- x O 2 mixed oxides. When x =0.1～0.5, amorphous CeTi 2O 6 phase mainly forms at 650 ℃ compared to the formation of CeTi 2O 6 which crystallizes at 800 ℃. When x >0.6, some TiO 2 enters the CeO 2 lattice and a CeO 2 TiO 2 solid solution is formed. The activity of 6%CuO/Ce x Ti 1- x O 2 calcined at 650 ℃ is largely affected by the x values, which is the highest when x =0.3, 0.4 and 0.9. The NO conversion reaches 70% at a reaction temperature of 150 ℃. By comparison, the x values have little effect on the activity of 6%CuO/Ce x Ti 1- x O 2 calcined at 800 ℃ . There are strong interactions between CuO and CeTi 2O 6, i.e., formation of the CeTi 2O 6 phase shifts the CuO reduction peak temperature from 380 to 200 ℃, and CuO, in turn, shifts the CeTi 2O 6 reduction peak temperature from 600 to 300 ℃.

Photocatalytic Degradation of Organics in Municipal Treated Wastewater in a Re-Circulation Reactor

In this paper, an experimental investigation on the effect of parameters namely concentration, solar radiation intensity and exposure time on the photo oxidation of pollutants in secondary treated municipal wastewater has been presented. TiO2 was used as the photo catalyst and the experiments were carried out in the month of February 2012 in Oman. The reactor was a glass tube constructed with the provision of adding a reflector. The results showed that photo catalytic treatment is very effective for dilute solutions and the presence of reflector enhances the photo degradation. The reduction in Chemical Oxygen Demand (COD) obtained at the experimental conditions of 0.007 m3/hr flow rate, 15°?inclination angle and 1 g·L-1?TiO2 dosage was 18%. The presence of the reflector increased the degradation to 25% at the above experimental conditions.

Kinetics Study on Photocatalytic Degradation of Methyl Orange Catalyzed by Sea Urchin-Like Cu2O

Sea urchin-like cuprous oxide with hollow glass microsphere as core was prepared using sodium sulfite as the reducing agent and sodium acetate-acetic acid as buffer solution in copper sulfate solution. Methyl orange was selected as degradation target for photocatalytic experiments. The photocatalytic activities were investigated by visible spectro- photometer. Photocatalytic kinetics parameters were studied by the Langmuir-Hinshelwood model and Arrhenius formula. It was observed that the sea urchin-like morphology dramatically improved the photocatalytic activity of cuprous oxide. The photo-degradation belongs to the first-order reaction and the maximum degradation rate could reach 94.37%. The activation energy and pre-exponential factor are 41.18 KJ·mol-1 and 1.07 × 106, respectively. After seven times recycling, the sample still showed high photo-catalytic efficiency and stability.

Synthesis of 3-(1-Cyclohexenyl)-2-butanone via Environmentally Friendly Catalysts

We substituted several environmentally friendly catalysts which included HY and H- β zeolites, various cation-exchanged β zeolites, and solid-supported ferric chloride for conventional catalysts for the synthesis of 3-(1-cyclohexenyl)-2-butanone from the reaction of ethylidenecyclohexane with acetic anhydride at room temperature. HY zeolite was found to be the most effective for this reaction, and gave the acylated product in a 72% yield under the conditions of n (ethylidenecyclohexane)/ n (acetic anhydride)/ m (HY zeolite)=1 mmol/10 mmol/0 100 g, reaction temperature 25 ℃ and reaction time 2 h. The used HY zeolite can be recovered, regenerated and gave almost the same yield as the fresh one. The lifetime of the HY zeolite is over 80 h. The effect of different factors on the reaction has also been investigated.