通过晶面调控产生强内建电场以提高卟啉光催化剂的H_(2)O_(2)生成速率

过氧化氢(H_(2)O_(2))是一种重要的化工产品,广泛应用于污水处理、消毒杀菌和印染漂白等领域.在蒽醌法生产H_(2)O_(2)的过程中,易产生有毒气体并存在爆炸危险.因此,仅利用水、氧气和太阳光即可在合适的光催化剂上生成H_(2)O_(2)的光催化技术备受关注.本课题组报道了通过酸碱自组装法制备的四(4-羧基苯基)卟啉(SA-TCPP)光催化剂,用于生产H_(2)O_(2).该催化剂克服了大部分H_(2)O_(2)光催化剂存在的需要牺牲剂、活性低和光利用率不足等问题,但其性能仍受限于较高的复合率.晶面调控已被证实是改善许多无机催化剂电荷复合的有效策略,然而,对于有机光催化剂,关于暴露晶面与其活性关系的研究仍然较少.本文采用溶解-重结晶法在水和三种有机溶剂的混合物中成功合成了三种具有不同暴露晶面的卟啉光催化剂.即利用卟啉在有机溶剂和水中的溶解度差异,将卟啉先溶解在四氢呋喃(THF)、甲醇(MeOH)或乙二醇(EG)溶液中,随后在水溶液中重新结晶.X射线衍射、高分辨率透射电子显微镜及晶面模拟模型图的结果表明,三种催化剂具有相同的晶体结构,但分别暴露了(400)、(022)和(020)晶面.通过紫外分光光度计测量这些催化剂在氙灯(λ≥420 nm)照射下的光催化活性,结果表明,具有(400)暴露面的卟啉光催化剂的H_(2)O_(2)生产速率最高,可达29.33 mmol L h^(-1)g^(-1),分别是具有(022)暴露面和(020)暴露面的卟啉光催化剂的2.7倍和4.1倍,约是已报道的SA-TCPP光催化剂的1.3倍.通过紫外漫反射、莫特肖特基曲线分析以及LED灯照射下的光催化活性测试,排除了光吸收能力对这三种卟啉光催化剂活性的影响.开尔文探针力显微镜、光生电流密度谱图、晶面模拟模型图和密度泛函理论计算结果表明,活性的差异主要归因于(400)表面暴露的高羧基含量所引发的强内建电场,并且在该暴露面上的内建电场方向有利于空穴从吡咯氮向羧基碳的跃迁,因此阻碍了电荷的快速重组,促进了富有挑战性的水氧化过程,而(020)面由于暴露了最多的吡咯氮和最少的羧基碳,其产生的内建电场强度最弱,且内建电场方向阻碍了空穴向羧基碳的跃迁,因此H_(2)O_(2)生产速率最低.综上所述,本工作通过晶面调控产生强内建电场以加速空穴的迁移,降低了电子空穴复合速率,实现了高H_(2)O_(2)生产速率,为更高效的有机光催化剂的设计和开发提供了新思路.

Analysis on Therapeutic Potential and Action Mechanism of Folium Pyrrosiae Based on Biolabel Pattern

[Objectives]The therapeutic potential and action mechanism of Folium Pyrrosiae were analyzed based on the biolabel pattern.[Methods]The chemical components of Folium Pyrrosiae were analyzed by liquid chromatography-mass spectrometry(LC-MS).Ten databases,including Pubchem,CTD,BindingDB,HERB,TCMIP,ETCM,SwissTargetPrediction,SuperPred webserver,TargetNet and SEA,were used in turn to retrieve the targets of related components,and key components were obtained according to the enrichment degree of targets.The obtained targets were imported into the STRING database to obtain PPI information and screen out core targets.The DAVID database was employed to analyze KEGG pathways of core targets and obtain key pathways.A key component-core target-key pathway network of Folium Pyrrosiae was constructed by Cytoscape3.10.1 software.The obtained KEGG pathways were input into the CTD database to predict corresponding diseases,and discussion and analysis were carried out.[Results]Ten key components,30 potential targets and 10 key pathways were screened out,and they participated in many diseases,of which five diseases were mainly analyzed.[Conclusions]Folium Pyrrosiae had the characteristic of multi-component,multi-target and multi-pathway synergistic effect in the treatment of lung cancer,type 2 diabetes,atherosclerosis,liver cancer,prostate cancer and other diseases,and the therapeutic potential and action mechanism of Folium Pyrrosiae were analyzed through the biolabel pattern.This study provides a research basis for further developing new functions of Folium Pyrrosiae.

Effect of cryostructures on the uniaxial compressive strength of frozen clay

Unconfined uniaxial compressive tests were performed to study the influence of cryostructure on frozen clay's behavior,such as strain-stress,compressive strength,and failure characteristics,at temperatures varying from-10 to-2°C and strain rates varying from 1.0×10-5to 1.0×10-3s-1.Artificial samples were prepared of three types:(1)integral structure,(2)laminar structure,and(3)reticular structure.The impact of temperature,strain rate,and cryostructure on the mechanical properties is discussed.In general,frozen clay with various cryostructures shows strain-softening behavior in the range of testing temperatures and strain rates.For frozen clay of different cryostructures,the ultimate compressive strength increases with increasing strain rate and decreasing temperature.Under the same testing conditions,the ultimate compressive strengths from high to low are in integral samples,laminar samples,and reticular samples.Failure strain of frozen clay generally increases with increasing temperature and does not indicate any correlation with cryostructure or strain rate.The failure mode of integral and reticular samples was shear failure,while laminar samples showed tensile failure.

Two-in-one tecton strategy to construct single crystalline hydrogen-bonded organic framework with high proton conductivity above 100℃

By tactically integrating two different kinds of proton donors and acceptors into one supramolecular tecton, a new crystalline hydrogen-bonded organic framework(HOF-SXU-1) has been developed. HOF-SXU-1 features a remarkable proton conductivity as high as 6.32 mS cm^(-1) and an extremely low activation energy of 0.16 eV at 160℃ under anhydrous N_(2) conditions.By contrast, under identical conditions, the organic precursors of HOF-SXU-1 only exhibit negligible proton conduction performance, demonstrating that the formation of HOF is crucial for excellent proton conduction performance.