Design of graphene-based TiO2 photocatalysts—a review

There is a recent increase in the interest of designing high-performance photocatalysts using graphene-based materials. This review gathers some important aspects of graphene?CTiO₂, graphene oxide?CTiO₂, and reduced graphene oxide?CTiO₂ composites, which are of especial relevance as next generation photocatalysts. The methods used for the preparation of these materials, the associated mechanistic fundamentals, and the application of graphene-based composites on the photocatalytic degradation of pollutants are reviewed. Some structural, textural, and chemical properties of these materials and other photo-assisted applications, such as hydrogen production from water splitting and dye-sensitized solar cells, are also briefly included.     

利用回收石墨制备的氧化石墨烯及其吸附性能

以浮选法从脱硫渣中回收的石墨为原料,采用HUMMERS法制备氧化石墨烯,并以阳离子艳红为目标污染物对氧化石墨烯的吸附性能进行研究。研究表明从脱硫渣中回收的石墨为鳞片石墨,与天然鳞片石墨在晶体结构、形貌等方面无明显差异。2种石墨经氧化后均形成了含有C-OH、-COOH和C-O-C等官能团的氧化石墨烯。氧化石墨烯对阳离子艳红的吸附速率非常快,在5 min后能达到吸附平衡,理论最大吸附量为714 mg·g-1,吸附过程符合Langmuir等温式。     

In vitro effects of acephate on carbonic anhydrase activity in the blood and gills of rainbow trout, Salmo gairdneri

Acephate, a water-soluble organophosphate pesticide used to control terrestrial insect pests, may enter aquatic ecosystems in the course of its use and adversely affect fish populations. The in vitro effects of this insecticide on gill and red blood cell (RBC) carbonic anyhdrase (CA) activity in rainbow trout were investigated over a range of 100 mg/1 (0.55 mM) to 50,000 mg/l (273 mM) to assess the manner in which acephate might affect respiratory capacity in exposed fish. Concentrations required to produce 50% inhibition of CA activity in the gill and RBC preparations were 38,000 mg/l (207 mM) and 8,900 mg/l (48 mM) respectively. The toxic action of acephate may be related to inhibition of CA activity in the blood and gills with resultant disturbances of respiratory capacity and salt balance.     

石墨烯氧化物气凝胶修饰金属阳极促进微生物燃料电池的产电性能

微生物燃料电池（microbial fuel cell,MFC）阳极的比表面积、生物相容性以及导电性被认为是影响微生物燃料电池产电性能的关键因素。三维金属阳极因其导电性强、比表面积较二维电极材料大等优点可用来取代碳基电极。为了提高微生物燃料电池的产电性能,本研究选用2种具有三维结构的不锈钢刷（SSB）和泡沫镍（Ni-foam）为金属阳极基材,并将石墨烯氧化物（GO）通过一步冷冻干燥法合成石墨烯氧化物气凝胶复合金属电极（GOA-SSB/Ni-foam）,将其作为阳极进行MFC的产电性能研究。结果显示：在MFC运行中,GOA-SSB和GOA-Ni-foam作为阳极,最大功率密度分别达到490和119 mW·m-2,比未修饰SSB和Ni-foam提高8.1和5.5倍。扫描电镜（SEM）表征显示三维复合金属阳极表面附着的微生物量远高于未修饰电极,且未修饰的SSB和Ni-foam电极表面较GOA-SSB和GOA-Ni-foam电极表面腐蚀更严重,说明GOA不仅可提升阳极比表面积、生物相容性还可减缓阳极基材的腐蚀。电化学阻抗（EIS）结果表明GOA-SSB和GOA-Ni-foam阳极相比于未修饰阳极能够极大的降低传荷电阻,证实GOA修饰阳极加快了电子传递速率。另外,拉曼（Raman）表征显示Shewanella oneidensis MR-1菌可原位还原GOA,佐证了GOA修饰阳极运行后欧姆内阻降低的原因。     

杀灭菊酯对鲤鱼血液影响初探

报道了杀灭菊酯杀虫剂对鲤鱼的血液系统的影响，结果表明，（１）杀灭菊酯引起鲤鱼血浆中离子浓度发生明显改变，Ｎａ＾＋下降１０％～２０％，Ｋ＾＋下降１０％～３５％，其它离子如Ｃｌ＾－，Ｃａ＾２＋，磷等则升高；同时还观察到Ｈｂ保持不变，（２）杀灭菊酯使ＲＢＣ渗透脆性增加，在体和体外处理均能引起ＲＢＣ破损，产生溶血，这很可能是杀灭菊酯对鱼类高毒的非神经作用的重要致毒原因之一。     

面向废水深度净化的氧化石墨烯膜过滤技术

膜过滤技术作为一种高效、低能耗、二次污染少的技术,已广泛用于工业废水的深度净化与再生中。传统有机膜在工业废水深度净化处理中存在着耐氧化性不足、使用条件苛刻、膜污染控制困难等问题。同时,膜过滤过程中产生的有机物/无机盐混合浓水也阻碍了浓水的资源化利用。氧化石墨烯膜作为下一代的膜材料具有更好的耐氧化性、亲水性,且制备成本低廉,对有机物与无机盐的分离性能优异,有望在工业废水的深度净化与回用中得到广泛应用。在阅读文献资料的基础上,梳理了氧化石墨烯膜的制备、性能特点,采用氧化石墨烯膜过滤技术进行工业废水深度净化的研究现状及尚待解决的问题,如材料的稳定性能及膜污染控制等。最后指出氧化石墨烯膜过滤技术在未来应逐步实现应用放大,并在工业废水深度净化、实现水与资源回用,达到近“零排放”的水处理过程中发挥重要作用。     

石墨烯/TiO2复合物的制备及其光催化性能

为拓展二氧化钛(TiO2)在可见光区的光响应范围,在140℃水热条件下制备了不同氧化石墨烯含量的石墨烯/二氧化钛(RGO/TiO2)复合材料。利用X-射线粉末衍射仪(XRD)、扫描电子显微镜(SEM)等对材料进行了表征。以甲基橙为目标污染物,研究了在模拟太阳光和紫外光照下TiO2和RGO/TiO2对甲基橙的光催化降解性能。结果表明,TiO2和GO复合后,TiO2由原来单一的金红石型转变为金红石型和锐钛矿型并存,出现了混晶效应;在模拟太阳光的条件下,复合材料的催化活性均高于TiO2本身;光照4 h后80 mg氧化石墨烯添加量制备的复合材料对甲基橙的光催化降解率达到69.58%,是TiO2的1.65倍;在紫外光照1.5 h时,复合材料对甲基橙的降解率达到了70%。由此可知,石墨烯的存在能够促进TiO2半导体中电子和空穴的有效分离,显著提高了TiO2光催化剂对可见光的响应。     

不锈钢纤维毡改性材料的制备及在微生物燃料电池中的应用

为制备一种导电性高、生物相容性良好且耐腐蚀的阳极材料,提高微生物燃料电池(MFC)的产电性能,以不锈钢纤维毡(SSFF)为基底,采用水热反应法制备了还原氧化石墨烯/不锈钢纤维毡(RGO/SSFF),并进一步采用粉体烧结法将纳米二氧化钛(TiO₂)负载至RGO/SSFF,制备了二氧化钛/还原氧化石墨烯/不锈钢纤维毡(TiO₂/RGO/SSFF),将SSFF(对照)、RGO/SSFF和TiO₂/RGO/SSFF分别作为MFC的阳极(对应的MFC分别命名为MFC-CK、MFC-RG和MFC-TRG)以探究改性材料对MFC去除水体中耗氧有机物和产电性能的影响。结果表明：与SSFF相比,RGO/SSFF和TiO₂/RGO/SSFF具有更大的电容(Q为413.9 mF和446.9 mF),更小的界面转移电阻(R_ct为19.65 Ω和18.16 Ω),更高的交换电流密度(i₀为1.56×10⁻⁵ mA和2.07×10⁻⁴ mA);MFC-TRG对水体COD去除速率最高可达929.62 mg·(L·d)⁻¹;MFC-RG和MFC-TRG稳定输出电压分别为245 mV和280 mV,比MFC-CK提高了88.5%和115.4%;MFC-RG和MFC-TRG的功率密度输出分别为 337.50 mW·m⁻²和472.03 mW·m⁻²,比MFC-CK提高了163.9%和233.9%。由此可知,改性后的RGO/SSFF和TiO₂/RGO/SSFF阳极成功提高了MFC的产电性能。该研究结果可为后续MFC阳极改性研究提供参考。     

Efficacy of vitamin-C (L-ascorbic acid) in reducing genotoxicity in fish (Oreochromis mossambicus) induced by ethyl methane sulphonate

The genotoxic effects of ethyl methane sulphonate (EMS) have been assessed in a fish, Oreochromis mossambicus with endpoints including chromosome aberrations, abnormal red blood cell nuclei, abnormal sperm morphology, and protein content (both qualitative and quantitative) of selected tissues, namely, muscle, heart, eye, brain, gill, liver, spleen and kidney. EMS caused chromosomal aberrations, nuclear anomalies in red blood cells, abnormal sperm morphology, and alteration of protein synthesis in various tissues. Some of the EMS toxicity appeared to be modulated and ameliorated in this fish by vitamin-C treatment.     

Bendiocarb effect on liver and central nervous system in the chick embryo

The aim of the study was to investigate toxicity of bendiocarb (2, 3-isopropyledene-dioxyphenyl methylcarbamate) to organs of chicken embryo. The toxic action of bendiocarb was observed on liver and central nervous system (CNS). Bendiocarb was administered to chicken embryos at embryonic day (ED) 3 in a dose 500 μ g/egg and 10 ED (800 μ g/egg). The observations showed no macroscopic or microscopic changes in the liver and CNS with either dose or day of incubation when the bendiocarb was administered. The liver and CNS were also investigated for caspase activity in relation to application of bendiocarb and no differences in the number of cells with caspase immunopositivity were observed in comparison with the control. The results obtained indicate that bendiocarb administered in the respective doses showed no toxicity to investigated organs. Furthermore, both at the early (3 ED) and the later (10 ED) stages of development no increase in numbers of apoptotic cells in chicken embryos was observed.     

Effect of methyl mercuric chloride treatment on haematological characteristics and erythrocyte morphology of Swiss mice

Effects of methyl mercuric chloride (MMC) on the blood parameters of Swiss mice (Mus musculus) were studied. The mice received an initial dose of MMC (24 mg kg(-1) body wt) as intraperitoneal injection followed by a second similar dose on the 14th day of the first dose administration. Significant (p < or = 0.001) decreases in haemoglobin content, red blood cell (RBC) count and haematocrit value were observed in the MMC injected mice when compared to the control mice. The effect of the second dose was severe, after which no significant recovery in the values of these parameters was observed. The result also showed a high degree of mercury accumulation in the blood of the MMC exposed mice. Interesting features were marked in the erythrocyte morphology of the exposed mice. An initial shrinkage followed by swelling of the cells was observed after each injection. The outline of the exposed cells was irregular with beak like or small finger like projections. Rupturing and disintegration of the erythrocyte membrane, leading to erythrolysis, were also noticed.     

Cadmium and copper heavy metal treatment from water resources by high-performance folic acid-graphene oxide nanocomposite adsorbent and evaluation of adsorptive mechanism using computational intelligence,isotherm, kinetic,and thermodynamic analyses

Environmental Science and Pollution Research - In this paper, folic acid–coated graphene oxide nanocomposite (FA-GO) is used as an adsorbent for the treatment of heavy metals including...     

Ag-石墨烯的制备及修饰电极对对苯二酚的电催化氧化

以石墨为原料,用改进的Hummers法制备了氧化石墨(GO),以葡萄糖为还原剂,采用一步还原法制备了Ag-石墨烯(Ag-Gr)纳米复合材料。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、热重分析(TGA)等手段对复合材料的结构及形貌进行了表征,并用循环伏安法考察了复合材料的电化学性能。结果表明:氧化石墨和银离子在葡萄糖的作用下,氧化石墨失去部分含氧官能团,被还原为石墨烯(Gr),银离子被还原为银纳米颗粒,均匀分布在石墨烯片层表面;在pH 值为7.0,Ag-石墨烯浓度为2.5 mg/mL时,Ag-石墨烯修饰玻碳电极对对苯二酚具有良好的电催化氧化作用。     

Oil spill cleanup using graphene

In this article, we study the use of thermally reduced graphene (TRG) for oil spill cleanup. TRG was synthesized by thermal exfoliation of graphite oxide and characterized by X-ray diffusion, Raman spectroscopy, SEM, TEM, elemental analysis, and Brunauer–Emmett–Teller (BET) surface area measurement. Various aspects of the sorption process have been studied including the sorption capacity, the recovery of the adsorbed oil, and the recyclability of TRG. Our results shows that TRG has a higher sorption capacity than any other carbon-based sorbents, with sorption capacity as high as 131 g of oil per gram TRG. With recovery of the sorbed oil via filtration and reuse of TRG for up to six cycles, 1 g of TRG collectively removes approximately 300 g of crude oil. Moreover, the effects of TRG bulk density, pore volume, and carbon/oxygen ratio and the oil viscosity on the sorption process are also discussed.     

Effects of mono-(2-ethylhexyl) phthalate (MEHP) on chicken germ cells cultured in vitro

In recent decades, many toxicological tests based on in vivo or in vitro models, mainly from mammalian (rat–mouse) and fish species, were used to assess the risks raised by contact or ingestion of molecules of pharmaceutical, agricultural, or natural origin. But no, or few, in vitro tests using other non-mammalian models such as bird have been explored despite their advantages: the embryonic gonads of birds have a high plasticity of development sensitive to estrogen, and sperm production is nearly two times faster than in rodents. Hence, we have established an in vitro culture of germ cells and somatic cells from chicken post-natal testis, and we have evaluated the sensitivity against the endocrine disruptor compound mono-(2-ethylhexyl) phthalate (MEHP) in comparison to previous studies using rodent and human models. After 96 h of exposure in presence of 10 μM MEHP, chicken seminiferous tubules cultures present a structural alteration, a reduction in cell proliferation and in germ cells population. Apoptosis of germ and somatic cells increases in presence of 1 μM MEHP. Furthermore, MEHP does not affect inhibin B and lactate production by Sertoli cells. These results are in accordance with previous studies using rat, mice, or human culture of testicular cells and in similar range of exposures or even better sensitivity for some “end-points” (biological parameters). In conclusion, the establishment of this postnatal testicular cells culture could be considered as an alternative method to in vivo experiments frequently used for evaluating the impact on the terrestrial wildlife species. This method could be also complementary to mammal model due to the limiting number of animals used and its elevated sensitivity.     

High-performance for hydrogen evolution and pollutant degradation of reduced graphene oxide/two-phase g-C<Subscript>3</Subscript>N<Subscript>4</Subscript> heterojunction photocatalysts

We have successfully synthesized the composites of two-phase g-C₃N₄ heterojunction photocatalysts by one-step method. And the reduced graphene oxide/two-phase g-C₃N₄ heterojunction photocatalyst was fabricated via a facile hydrothermal reduction method. The characterization results indicated that the two-phase g-C₃N₄ was integrated closely, and the common phenomenon of agglomeration for g-C₃N₄ was significantly reduced. Moreover, the oxidized graphene was reduced successfully in the composites and the graphene was overlaid on the surface or the interlayers of g-C₃N₄ heterojunction composite uniformly. In addition, we have carried out the photocatalytic activity experiments by H₂ evolution and rhodamine B removal, tetracycline removal under the visible light irradiation. The results revealed that the composite has improved the separation efficiency a lot than the pure photocatalyst. The photocurrent test demonstrated that the recombination of electrons and holes were efficiently inhibited as well as enhanced the photocatalytic activity. The 0.4% rGO loaded samples, 0.4% rGOCN2, own the best performance. Its rate of H₂ evolution was 15 times as high as that of the pure g-C₃N₄.     

磁性还原氧化石墨烯负载Fe0对罗丹明B的类芬顿降解

合成了磁性还原氧化石墨烯负载零价纳米铁材料（Fe0-MF-RGO）,并在双氧水（H2O2）的作用下构成类芬顿试剂用于对罗丹明B（RhB）的吸附-催化降解。通过正交实验研究了pH值、Fe0-MF-RGO用量、RhB初始浓度、温度和H2O2浓度5个影响因素。在15 ℃、pH值为7.0、Fe0-MF-RGO投加量1.0 g·L-1、RhB初始浓度为50 mg·L-1以及H2O2浓度为0.8 mmol·L-1的条件下,150 min后模拟废水中RhB的去除率达到98.17%,经5次循环使用后去除率为72.97%。     

TiO2-rGO制备及其对亚甲基蓝溶液的降解

本实验用改进的Hummers法制备氧化石墨烯(GO),通过溶胶-凝胶法制备得到TiO2-石墨烯复合材料(TiO2-rGO),研究了不同制备条件对复合材料光催化性能的影响。采用X射线衍射(XRD),拉曼光谱(Raman),比表面积(BET),扫描电镜(SEM),透射电镜(TEM)、紫外-可见(UV-Vis)吸收光谱和荧光光谱(PL)等测试手段对复合材料进行表征。结果表明,TiO2-rGO复合材料中的TiO2为锐钛相,且能均匀附着在石墨烯片层上,呈现层状堆积结构;与纯TiO2相比,复合材料具有较大的比表面积和更高的可见光响应。研究了该复合催化剂在紫外光下对亚甲基蓝以降解效果。当焙烧温度为450℃、TiO2/GO质量比为125:1时,制备得到的TiO2-rGO具有最优的光催化效果。     

Application of the comet and micronucleus assays to butterfish (Pholis gunnellus) erythrocytes from the Firth of Forth, Scotland.

This report describes an investigation of genotoxic effects in an inter-tidal fish species sampled along a pollution gradient in the Firth of Forth, Scotland, UK. The comet assay is an electrophoretic technique for measuring DNA breakage in nuclei from individual cells and has only recently been applied to field investigations of genotoxicity. The measurement of nuclear anomalies (NA), such as the presence of micronuclei (MN) and 'lobes', has been successfully utilised in many field studies of genotoxic effects of contaminated sediments. These two techniques were applied to nucleated red blood cells (RBC) from the butterfish, Pholis gunnellus. The comet assay was adapted and validated for use in this species. Fish were sampled from the inner Firth of Forth, which has a legacy of industrial contamination and the outer Firth of Forth which is comparatively clean. The analysis of DNA strand breakage using this technique did not reveal any significant differences between animals sampled from inner and outer zones of the Firth. In contrast, MN and NA frequencies were elevated in the inner polluted zone of the Firth compared to the outer zone. This study suggests: (1) there are genotoxic effects associated with contaminants in the inner Firth of Forth, and (2) the comet assay may not be a suitable genotoxicity biomarker in fish.     

Atrazine effects on in vitro maturation and in vitro fertilization in the bovine oocyte

The effect of low levels of atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) on in vitro oocyte maturation, in vitro capacitation of sperm, or in vitro fertilization of bovine oocytes and on the quality of blastocyst formation was studied. Bovine oocytes collected from abattoir ovaries were matured, fertilized, and developed to the blastocyst stage in vitro. Embryos that reached a morula or blastocyst stage were stained with Hoechst 33258 stain to determine the number of blastomeres per embryo. Three bulls whose fertilization rates were proven consistent among straws were used for this study. Atrazine was tested at concentrations of 0.01, 0.1, 1, and 10 microM in either the maturation medium, sperm capacitation medium, or the fertilization medium. Because atrazine was dissolved in ethanol, an ethanol control was used to determine any possible effects of ethanol on the in vitro process. The addition of atrazine to both the maturation and fertilization media did not result in any significant difference in fertilization rates between the controls and the treatments. In the capacitation medium, a significant difference between the controls and the atrazine levels of 0.1, 1, and 10 microM was noted for one bull. Atrazine did not affect the number of blastomeres per embryo. There was not a significant difference (p>0.05) in the number of blastomeres per embryo between the controls and the different levels of atrazine in each medium. This study indicates that low levels of atrazine do not have an effect on in vitro fertilization rates or the number of blastomeres per embryo produced in vitro.