新型MIL-101(Fe)/BiOBr S型异质催化剂用于高效光催化降解抗生素和还原六价铬:光催化性能分析和光催化机理研究

水污染对生态环境和人类健康造成了巨大危害,特别是水体中抗生素和重金属具有毒性且难生物降解,已经引起科研工作者的广泛关注.传统的水处理技术难以有效地消除这些污染物.近年来,人们致力于开发绿色、低碳且高效的光催化技术用于解决环境污染问题,该技术实现大规模应用的核心在于开发出经济、高效的光催化剂.由于单一半导体光催化材料(如BiOBr)存在一些缺陷(如有限的催化活性位点和光生电子-空穴快速复合等),因此,构建具有可见光响应、高暴露活性位点和强氧化还原能力的异质结特别是新兴的梯(S)型异质结是去除这些污染物的有效策略之一.MIL-101(Fe)是一种新型的可见光驱动的金属-有机配体框架材料,具有强还原活性、高比表面积和较好的可见光吸收能力,因此,将氧化型的Bi OBr与还原型的MIL-101(Fe)进行合理设计,构筑S型异质结,有望开发出高效的催化材料.本文采用溶剂热法成功制备了一种新型的MOF基S型异质结MIL-101(Fe)/BiOBr,用于可见光照射下光催化还原六价铬(Cr(Ⅵ))和降解抗生素恩诺沙星.结果表明,在单一污染物体系中,MIL-101(Fe)/BiOBr可有效还原99.4%的Cr(Ⅵ)和氧化分解84.4%的恩诺沙星.值得注意的是,在Cr(Ⅵ)和恩诺沙星共存的条件下,MIL-101(Fe)/BiOBr对(Cr(Ⅵ))和恩诺沙星的去除效率明显提升,这主要是由于S型催化剂、Cr(Ⅵ)和恩诺沙星之间具有协同效应.MIL-101(Fe)/BiOBr催化剂活性增强的主要因素如下:(1)MIL-101(Fe)提供了大量的活性位点,改善了催化材料的光吸收能力.(2)S型载流子分离路径不但促进了电子和空穴的高效分离,而且增强了体系的氧化还原能力.此外,采用自由基捕获实验、电子自旋共振波谱仪、液相色谱-质谱联用技术以及毒性分析软件,系统分析了光催化反应机理、抗生素分解过程和中间产物的生物毒性.综上,本文提供一种简单有效的策略来构筑高活性的MOF/无机半导体S型异质结材料用于高效净化水体环境.

新型氮氧化钽/氧空位钨酸铋S型异质结纤维用于高效光催化降解抗生素和还原六价铬:产物毒性分析和光催化机理研究

近年来,环境污染问题严重地威胁着人类的生存和健康.半导体光催化是一种绿色环保的治理环境污染技术,该技术实现大规模应用的关键在于构建高效的光催化剂.TaON因优异的光电性质、稳定的物理化学性质及适合的能带结构等优势,被广泛应用于光催化水裂解和有害污染物降解等领域.但光生载流子快速复合和比表面积小等问题严重制约了其大规模应用.近年来,人们发现构建新型S型异质结能有效促进光生电子和空穴分离,同时充分保存具有强氧化还原能力的电子和空穴,进而有效提升材料的光催化性能.因此,通过构建新型TaON S型异质结光催化材料有f望开发出高效的可见光光催化体系.本文采用静电纺丝-煅烧-氮化工艺制备出由纳米颗粒组成的多孔TaON纳米纤维,然后采用溶剂热法制得一系列富含氧空位的TaON/Bi_(2)WO_(6) S型异质结纤维,并用于可见光照射下光催化降解抗生素和还原Cr^(6+).实验发现,富含氧空位的Bi_(2)WO_(6)二维纳米片均匀生长在TaON纳米纤维上形成了良好的1D/2D核壳结构,此异质结界面结构有利于界面间电荷的分离和传输.当TaON/Bi_(2)WO_(6)质量比为20 wt%时,在可见光下分别照射50,60和50 min,20 mg复合纤维可降解93.2%的四环素溶液(20 mg/L,100 mL,pH=5.2),83.7%的左氧氟沙星溶液(20 mg/L,100 mL,pH 6.7)以及还原95.6%的Cr^(6+)溶液(10 mg/L,100 mL,pH=2.5),其对三种污染物的去除速率分别是纯Bi_(2)WO_(6)的3.8,2和2.9倍,且远高于纯TaON纤维.此外,该复合纤维具有良好的矿化能力及循环稳定性,在实际废水中依然表现出较好的催化降解活性.表征结果表明,复合纤维光催化活性增强是由于TaON与Bi_(2)WO_(6)之间形成了S型的异质结,并富含氧空位;在内电场,能带弯曲和库仑力的协同作用下,实现了强氧化还原能力的电子和空穴的高效分离和保存,有效提升了体系的光催化性能.综上,本文采用缺陷工程结合异质构筑策略有效地提升了体系的光催化活性,为开发高效的光催化体系提供一定的参考.

Effects of dietary tributyrin on intestinal mucosa development,mitochondrial function and AMPK-mTOR pathway in weaned pigs

Background:The objective of this experiment was to investigate the influence of dietary tributyrin on intestinal mucosa development,oxidative stress,mitochondrial function and AMPK-mTOR signaling pathway.Methods:Seventy-two pigs were divided into two treatments and received either a basal diet or the same diet supplemented with 750 mg/kg tributyrin.Each treatment has six replicates of six pigs.After 14 days,6 pigs from each treatment were selected and the jejunal samples were collected.Results:Results showed that supplemental tributyrin increased(P<0.05)villus height and villus height:crypt depth of weaned pigs.Pigs fed tributyrin had greater(P<0.05)RNA/DNA and protein/DNA ratios than pigs on the control group.The mRNA levels of sodium glucose transport protein-1 and glucose transporter-2 in the jejunum were upregulated(P<0.05)in pigs fed the tributyrin diet.Dietary tributyrin supplementation lowered(P<0.05)the malondialdehyde and hydrogen peroxide(H2O2)content in jejunum,enhanced(P<0.05)the mitochondrial function,as demonstrated by decreased(P<0.05)reactive oxygen species level and increased(P<0.05)mitochondrial membrane potential.Furthermore,tributyrin increased(P<0.05)mitochondrial DNA content and the mRNA abundance of genes related to mitochondrial functions,including peroxisomal proliferator-activated receptor-γcoactivator-1α,mitochondrial transcription factor A,nuclear respiratory factor-1 in the jejunum.Supplementation with tributyrin elevated(P<0.05)the phosphorylation level of AMPK and inhibited(P<0.05)the phosphorylation level of mTOR in jejunum compared with the control group.Conclusions:These findings suggest that dietary supplementation with tributyrin promotes intestinal mucosa growth,extenuates oxidative stress,improves mitochondrial function and modulates the AMPK-mTOR signal pathway of weaned pigs.

Preparation, characterization, antimicrobial and cytotoxicity studies of copper/zincloaded montmorillonite

Background： A series of modified montmorillonites（Mt） including zinc-loaded Mt（Zn-Mt）, copper-loaded Mt（Cu-Mt）, copper/zinc-loaded Mt with different Cu/Zn ratio（Cu/Zn-Mt-1, Cu/Zn-Mt-2, Cu/Zn-Mt-3） were prepared by an ion-exchange reaction, and characterized using X-ray diffraction（XRD）, fourier transformed infrared spectroscopy（FTIR） and transmission electron microscopy（TEM）. The specific surface areas, antimicrobial activity and cytotoxicity of the modified Mt were investigated.Results： In the modified Mt, hydrated Cu ions and Zn ions were exchanged in the interlayer space of Mt and the particles were irregular shapes. The results showed that Cu/Zn-Mt enhanced antibacterial and antifungal activity compared with Zn-Mt and Cu-Mt possibly due to the synergistic effect between Cu and Zn. Among the Cu/Zn-Mt with different Cu/Zn raitos, Cu/Zn-Mt with a Cu/Zn ratio of 0.98 or 0.51 showed higher antimicrobial activity against gram-negative bacteria（Escherichia coli）, gram-positive bacteria（Staphylococcus aureus）, fungi（Candida albicans）.Moreover, the antimicrobial activity of Cu/Zn-Mt was correlated with its specific surface area. Cytotoxicity studies on IPEC-J2 cell showed a slight cytotoxicity of Cu/Zn-Mt.Conclusions： The current data provide clear evidence that in terms of its antimicrobial activity and relatively low toxicity, the Cu/Zn-Mt holds great promise for applications in animal husbandry.

碳量子点/四(4-羧基苯基)卟啉/BiOBr S型异质结用于高效光催化降解抗生素

太阳能光催化处理制药废水是缓解环境问题和能源危机的一种很有前途的方法.然而,提高其处理效率面临众多挑战,如光吸收效率低、光生载流子快速复合和光氧化还原电位低等.本文通过在BiOBr(BOB)微球上沉积碳量子点(CDs)和四(4-羧基苯基)卟啉(TCPP),巧妙地构建了TCPP/CDs/BOB有机/无机三元S型异质结,用于在可见光下有效降解水体中的盐酸四环素(TC).研究发现,由于两者之间的费米能级差异,在形成异质结时触发了电子从TCPP传递到BOB,从而在界面处构建内部电场(IEF).这极大推动了光诱导载流子的有效分离.此外,CDs作为电子收集器进一步提高了S型异质结的载流子分离能力,因此保留了在CDs中聚集更强还原能力的光电子和在BOB价带中更强氧化能力的空穴来参与光催化反应.在这些催化剂中,TCPP/CDs/BOB-2异质结催化剂在40 min内对TC的降解能力高达83.6%.TCPP/CDs/BOB-2的反应速率常数(k)分别约为BOB、CDs/BOB和TCPP/BOB的2.3、1.8和2.0倍.这项工作为探索用于水净化的有机/无机三元S型光催化剂提供了新的视角.

Ta_(3)N_(5)/CdS Core–Shell S‑scheme Heterojunction Nanofibers for Efficient Photocatalytic Removal of Antibiotic Tetracycline and Cr(VI):Performance and Mechanism Insights

Ta_(3)N_(5)/CdS core–shell S-scheme heterojunction nanofibers are fabricated by in situ growing CdS nanodots on Ta_(3)N_(5) nanofib-ers via a simple wet-chemical method.These Ta_(3)N_(5)/CdS nanofibers not only affords superior photocatalytic tetracycline degradation and mineralization performance,but also cause an efficient photocatalytic Cr(VI)reduction performance.The creation of favorable core–shell fiber-shaped S-scheme hetero-structure with tightly contacted interface and the maximum interface contact area promises the effective photo-carrier disintegration and the optimal photo-redox capacity synchronously,thus leading to the preeminent photo-redox ability.Some critical environmental factors on the photo-behavior of Ta_(3)N_(5)/CdS are also evaluated in view of the complexity of the authentic aquatic environment.The degradation products of tetracycline were confirmed by HPLC–MS analyses.Furthermore,the effective decline in eco-toxicity of TC intermediates is confirmed by QSAR calculation.This work provides cutting-edge guidelines for the design of high-performance Ta_(3)N_(5)-based S-scheme heterojunction nanofibers for environment restoration.

富含氧空位S型MIL-101(Fe)/BiOCl异质结增强光催化去除Cr(Ⅵ)

Cr(Ⅵ)污染物有毒有害且不可生物降解,会对环境造成严重破坏。光催化技术可实现Cr(Ⅵ)的有效去除,在解决环境污染问题方面具有良好前景。因此,本文通过在富含氧空位(OV)的BiOCl微球表面原位生长MIL-101(Fe)晶体,构建了一种新型富氧缺陷MOF基S型异质结催化剂-MIL1--101(Fe)/BiOCl。这种催化剂在高浓度Cr(Ⅵ)的光催化还原中表现出优异活性,60 min内对Cr(Ⅵ)溶液(10 mg·L^(-1),100 mL)的光还原效率达到88.5%,其光催化效率分别是BiOCl和MIL-101(Fe)的4.4和9.0倍。而且,MIL-101(Fe)/BiOCl还表现出良好的抗环境干扰性、稳定性和可重复使用性,显示出令人印象深刻的实际应用前景。实验结果表明,富含氧空位的S型MIL-101(Fe)/BiOCl异质结构暴露了大量活性位点,促进了界面电荷分离,提高了光生载流子的氧化还原能力,从而增强了光催化性能。另外,经过活性自由基检测发现,e^(-)和·O_(2)^(-)是光催化反应过程中的主要活性物种。这些研究结果将为开发用于环境治理的缺陷半导体/MOF S型光催化剂开辟新的途径。

Rationally designed Ta_(3)N_(5)/BiOCl S-scheme heterojunction with oxygen vacancies for elimination of tetracycline antibiotic and Cr(Ⅵ):Performance,toxicity evaluation and mechanism insight

S-scheme heterojunction photocatalysts have been the“stars”in the field of photocatalysis.Herein,a novel S-scheme heterojunction of Ta_(3)N_(5)/BiOCl with oxygen vacancies(OVs)was fabricated via a facile method.The charge separation and transport mechanism of this Ta_(3)N_(5)/BiOCl S-scheme heterojunction was verified by the analyses of band energy structures,active species,photoelectric behaviors and DFT theoretical calculation.Compared with Ta_(3)N_(5)and BiOCl,the Ta_(3)N_(5)/BiOCl unveils substantially upgraded photocatalytic property under visible light,and the photocatalytic efficiency for removal of tetracycline(TC)and hexavalent chromium(Cr(VI))reaches 89.6%and 91.6%,respectively.The substantial enhancement of the photocatalytic activity is attributed to the synergistic effect of the S-scheme hetero-structure and oxygen vacancies,which improves the visible-light absorption,while promoting the spatial separation of charge carriers with the optimum redox capacity,thereby boosting the production of active species for catalytic reactions.The TC degradation pathway is deduced and the toxicity evolution of TC is appraised using the QSAR method.In a nutshell,this work gives a deep understanding of the photocatalytic mechanism based on Ta_(3)N_(5)/BiOCl as well as presents a newfangled thought for developing highly efficient S-scheme heterojunction photocatalysts for water decontamination.