TiO2纳米粒子气固相光催化降解乙烯初探

该文对TiO2纳米粒子气固光催化降解果蔬贮藏环境乙烯技术进行了初步研究.采用溶胶-凝胶法制备的纳米TiO2薄膜作光催化剂,利用自行设计的气固光催化实验系统,研究了乙烯浓度、紫外光作用时间对光催化降解反应的影响,探讨了乙烯的光催化降解的动力学.结果显示:该研究所制备的TiO2锐钛矿型含量为48.766%,比表面积为47.186 m2/g,具有良好的光催化性能;光催化降解乙烯比直接紫外线光降解效果显著,光照10 min时光催化乙烯降解率比直接紫外线光降解提高23.76%;乙烯的降解率随着其浓度的增加而降低;乙烯的光催化降解的动力学可以用Langmuir-Hinshelwood动力学方程加以描述.     

纳米TiO2光半导体材料防治植物病害的初步研究

纳米TiO₂光半导体材料是一种具有抗菌与环境净化功能的新型环境友好材料，试验首次探索了将其应用于植物病害防治的可能性。在黄瓜霜霉病防治研究的栽培试验中发现，喷施纳米TiO₂光半导体溶胶材料可以显著地降低黄瓜霜霉病的发病率和病情指数，减少叶片病斑数量与病斑面积。试验研究结果初步证实了其对黄瓜霜霉病害具有一定的防治作用，为以纳米TiO₂光半导体溶胶材料为主要有效成分的植物抗菌剂与保护剂的开发提供了参考依据。     

不锈钢基体上TiO2陶瓷膜的制备

作者对不锈钢基体上TiO₂陶瓷膜的制备技术进行了探索。试验以304不锈钢片为基体，采用溶胶－凝胶法在其表面制备TiO₂陶瓷膜层，探讨了溶胶的浓度、pH值、黏合剂和烧结温度对TiO₂膜层形貌的影响，并利用X射线衍射技术(XRD)研究了膜层的物相结构。结果表明，添加1%的聚乙烯醇(PVA1750)黏合剂于浓度0.07M、pH2.0的溶胶中制得涂膜液，用该涂膜液浸涂304不锈钢片，干燥后于600℃烧结，可以得到均匀的片状结构TiO₂陶瓷膜，经XRD分析，该膜层以金红石相为主，另含少量锐钛矿相；添加0.3%的甲基纤维素(MC)黏合剂于浓度0.07M的溶胶中，用该溶胶浸涂304不锈钢片，干燥后于700℃烧结，得到纯金红石相的颗粒状TiO₂陶瓷膜层。添加两种不同黏合剂的溶胶均可在不锈钢表面形成连续的TiO₂陶瓷膜层，但两者的添加量不同，需要的烧结温度也不同，所得的物相结构及形貌亦不同。两种不同形貌的片状及颗粒结构之间分别形成较为均匀的孔隙，可以作为过滤时的截留孔。     

纳米TiO2光催化降解有机磷农药的研究

通过实验，探讨了用纳米TiO2光催化处理有机磷农药模拟废水和实际应用的有机磷农药的可行性，实验表明，以测定不同时间PO4^3-的浓度来衡量有机磷的降解率，并以此来衡量有机农药及其中间产物降解的程度是合理的，光催化降解甲胺磷和水胺硫磷的结果，显示了有机磷农药的降解率与其结构有关，实际应用的有机磷农药也可用光催化降解。     

ZnO纳米粒子光催化降解失效农药草甘膦的研究

采用Zn（NO3）2.6H2O和CF3COONa为原料制备ZnO纳米材料,运用扫描电子显微镜（SEM）、X射线衍射仪（XRD）和紫外-可见漫反射光谱（UV-VisDRS）测定等技术对其进行表征。ZnO纳米粒子在波长为200～400nm的紫外光范围内具有强吸收,以高压汞灯为光源,利用ZnO纳米催化剂对失效农药草甘膦（FGP）进行光降解实验。研究表明,在经900℃煅烧的ZnO纳米粒子浓度为0.5g.L-1,FGP试液初始pH=2.2的条件下,光催化降解90min后FGP去除率达91.8%;光催化体系中,引入Fe3＋有利于提升ZnO纳米粒子催化活性。光谱分析显示,经ZnO纳米粒子光催化,失效农药草甘膦基本降解。     

60Co-g辐照改性银掺杂纳米TiO2及光催化降解乙烯

为了解60Co-射线辐照且以活性炭纤维(ACF)为载体所负载TiO2的半导体材料(TiO2/ACF)对光催化降解冷藏环境中乙烯的影响,该文拟采用60Co-辐照制备纳米Ag沉积的TiO2/ACF(Ag-TiO2/ACF)光催化材料,在模拟园艺产品的冷藏环境中,进行了3种不同膜的光催化降解乙烯效果的研究,并利用场发射扫描电镜(FESEM)、透射电子显微镜(TEM)、X射线衍射仪(XRD)对所制备的光催化材料进行相关的表征分析。结果表明:在加入分散剂聚乙烯吡咯烷酮后,60Co-辐照能使Ag颗粒较好地负载在TiO2上,TiO2均匀分散在ACF膜上而不发生团聚,且TiO2颗粒晶相改变、尺寸变小,有助于提高Ag-TiO2/ACF的催化效率。Ag-TiO2/ACF光催化降解乙烯的效果用一级动力学速率方程描述;经辐照制备的Ag-TiO2/ACF薄膜比未辐照的TiO2/ACF和辐照的TiO2/ACF薄膜光催化降解乙烯的反应速率常数分别提高了44%和37%。研究结果为TiO2光催化技术的进一步的应用提供了参考。     

典型菜地土壤剖面N2O、CH4与CO2分布特征研究

为探究菜地土壤剖面N2O、CH4与CO2时空分布特征,利用地下气体原位采集系统与气相色谱法,周年动态监测3种典型菜地,即休闲裸地、轮作地Ⅰ(芹菜?空心菜?小白菜?苋菜)以及轮作地Ⅱ(菜心?芹菜?空心菜?大青菜)7 cm、15 cm、30 cm与50 cm土层N2O、CH4与CO2浓度变化。结果表明,0~50 cm土层范围内,N2O、CH4与CO2 3种气体浓度周年变异性较大,变幅分别为0.63~1 657.0μL(N2O)?L?1、0.8~72.5μL(CH4)?L?1和0.41~36.6 m L(CO2)?L?1。轮作地Ⅰ与轮作地Ⅱ的N2O平均浓度随土壤深度增加而增加,休闲裸地则呈现先增加(0~30 cm)后降低(30~50 cm)的变化趋势。两种轮作菜地4个土层N2O平均浓度均显著高于休闲裸地,二者氮肥施用量不同并未造成相同土层间N2O平均浓度的显著差异。3种菜地CH4与CO2平均浓度均呈现50 cm30 cm15 cm7 cm的梯度特征。轮作地Ⅰ与轮作地Ⅱ0~15 cm土层CH4平均浓度均大于休闲裸地,而在15~50 cm土层则分别大于和小于休闲裸地。CO2浓度呈现明显的季节性变化,除轮作地Ⅰ50 cm土层外,两种轮作菜地其他土层CO2平均浓度均小于休闲裸地对应土层。可见,蔬菜地高氮肥施用、多频次耕作等复杂管理使得N2O、CH4与CO2表现出较大的时空变异特征,其中氮肥施用对N2O的影响大于CH4与CO2,CH4受施肥与耕作的影响均较小,CO2显著受土壤温度与耕作措施的影响,在此基础上需进一步探究N2O、CH4与CO2的其他影响因素。     

60Co-γ辐照改性银掺杂纳米TiO2及光催化降解乙烯

为了解60Co-γ射线辐照且以活性炭纤维(ACF)为载体所负载TiO2的半导体材料(TiO2/ACF)对光催化降解冷藏环境中乙烯的影响,该文拟采用60Co-γ辐照制备纳米Ag沉积的TiO2/ACF (Ag-TiO2/ACF)光催化材料,在模拟园艺产品的冷藏环境中,进行了3种不同膜的光催化降解乙烯效果的研究,并利用场发射扫描电镜(FESEM)、透射电子显微镜(TEM)、X射线衍射仪(XRD)对所制备的光催化材料进行相关的表征分析.结果表明:在加入分散剂聚乙烯吡咯烷酮后,60C0-γ辐照能使Ag颗粒较好地负载在TiO2上,TiO2均匀分散在ACF膜上而不发生团聚,且TiO2颗粒晶相改变、尺寸变小,有助于提高Ag-TiO2/ACF的催化效率.Ag-TiO2/ACF光催化降解乙烯的效果用一级动力学速率方程描述;经辐照制备的Ag-TiO2/ACF薄膜比未辐照的TiO2/ACF和辐照的TiO2/ACF薄膜光催化降解乙烯的反应速率常数分别提高了44％和37％.研究结果为TiO2光催化技术的进一步的应用提供了参考.     

纤维素降解菌对农业有机废弃物发酵进行CO2施肥的作用

采用室内培养和大棚试验相结合,对分离的3种纤维素降解菌在有机废弃物发酵释放CO₂中的作用及其对增加大棚CO₂浓度的效果进行了研究。结果表明,分离获得的三种菌均能明显促进有机废弃物发酵CO₂的释放,其中菌A和菌C的效果优于菌B;3种菌混合接种时效果最佳。在大棚栽培条件下,昼间CO₂浓度大部分时间低于300μL/L,处于亏缺状态;采用棚中不接种直接发酵也可大幅提高大棚的CO₂浓度,但释放的时间只有9.d左右;采用3种菌混合接种的方法棚内全天维持CO₂浓度800μL/L以上的时间可达14.d以上。     

我国能源消费与CO2排放的系统动力学预测

目前我国正处在全面建设小康社会的重要发展阶段。在人口总量增加、经济持续发展、居民生活能源消费不断提高的情况下,对能源供需状况进行科学、合理的预测对保障我国能源供给、促进经济可持续发展和CO₂减排,实现社会可持续发展具有重要意义。本文在研究我国现阶段能源消费和人口、经济发展现状的基础上,运用系统动力学模型预测了我国能源需求和CO₂排放量,提出能源发展和削减CO₂排放量的设想和对策。     

A new technique to measure soil CO2 efflux at constant CO2 concentration

A new principle for measuring soil CO₂ efflux at constant ambient concentration is introduced. The measuring principle relies on the continuous absorption of CO₂ within the system to achieve a constant CO₂ concentration inside the soil chamber at ambient level, thus balancing the amount of CO₂ entering the soil chamber by diffusion from the soil. We report results that show reliable soil CO₂ efflux measurements with the new system. The novel measuring principle does not disturb the natural gradient of CO₂ within the soil, while allowing for continuous capture of the CO₂ released from the soil. It therefore holds great potential for application in simultaneous measurements of soil CO₂ efflux and its δ¹³C, since both variables show sensitivity to a distortion of the soil CO₂ profile commonly found in conventional chamber techniques.     

碳酸氧镧改性生物炭材料的合成及对磷酸盐去除性能

为高效去除废水中过量的磷酸盐为目的,该研究将研究利用艾草生物质与镧溶液共生共热的方法制成具有大量纳米级碳酸氧镧突起的镧基复合生物炭材料,研究了材料投加量、初始磷酸盐浓度、吸附时间、初始溶液pH值和共存离子对其吸附磷酸盐性能的影响及饱和磷吸附镧基复合生物炭材料（La-CB2-P）对生菜种子发芽率的试验。试验结果表明：La-CB2最佳投加量为1 g/L,最佳吸附温度为25 ℃,对磷酸盐的吸附主要为多分子层吸附,Langmuir模型模拟最大吸附容量为126.82 mg/g,并在12h内达到吸附平衡,酸性至中性水环境中La-CB2吸附性能更优,并对碱性水环境的pH值具有缓冲作用,在pH值为3时La³⁺浸出率为7.66%,其他pH值条件下仅为0.029%左右,在磷吸附过程中La-CB2的DOC溶出量随着初始溶液pH值的升高呈先增后减的趋势,在多种共存阴离子中对磷酸盐具有很强的选择性吸附,水体中的腐殖酸会大幅度降低La-CB2对磷酸盐的吸附性能。饱和磷吸附镧基复合生物炭材料（La-CB2-P）能够作为磷缓释肥显著促进生菜发芽,对La-CB2在富营养水体的磷吸附及资源回收提供了大量的理论基础。     

方波脉冲电压提高光催化降解乙烯反应器性能

为了解以活性炭纤维(activated carbon fiber,ACF)为载体负载Ag沉积TiO2的光电极膜材料((Ag+TiO2)/ACF)在方波脉冲电压(pulsed direct current DC square-wave,PDCSW)下光催化降解冷藏环境中乙烯的效率,该文以自行研制的乙烯反应器为研究对象,该反应器的电压源以数字信号处理器(digital signal processor,DSP)为核心,控制输出方波的幅值、占空比和频率等高精确参数值。试验对催化后的光电极膜材料进行X射线能谱分析(energy dispersive x-ray spectroscopy,EDS)表征,结果表明,方波脉冲作用后对光电极破坏较小,Ag的脱落情况不明显。试验展开直流电压源(direct-current power,DC)和方波脉冲电压源下光电催化降解乙烯效率的比较。结果表明,方波脉冲下乙烯降解速率常数K值2.296×10-4 min-1较直流下K值1.715×10-4 min-1更大,有较高的催化效率。研究了方波电压、占空比和频率对降解乙烯效率的影响,采用二次旋转组合试验和回归拟合,建立了乙烯降解速率常数(K)与参数关系的二次多项式数学模型,验证了模型的有效性,结果表明,随着方波电压不断增大,乙烯的降解速率呈现先增大后减小的趋势,占空比和频率对降解乙烯的影响呈现出与电压同样的变化趋势。利用数学模型找出最优参数组合,电压25.5 V,占空比23%,频率310 Hz,最优K值为0.0002783 min-1。该研究为方波脉冲电压辅助光催化技术的应用和进一步的研究提供科学依据。     

Elevated CO2 concentration and nitrogen fertilisation effects on N2O and CH4 fluxes and biomass production of Phleum pratense on farmed peat soil

The effects of elevated CO₂ supply on N₂O and CH₄ fluxes and biomass production of Phleum pratense were studied in a greenhouse experiment. Three sets of 12 farmed peat soil mesocosms (10 cm dia, 47 cm long) sown with P. pratense and equally distributed in four thermo-controlled greenhouses were fertilised with a commercial fertiliser in order to add 2, 6 or 10 g N m⁻². In two of the greenhouses, CO₂ concentration was kept at atmospheric concentration (360 μmol mol⁻¹) and in the other two at doubled concentration (720 μmol mol⁻¹). Soil temperature was kept at 15 °C and air temperature at 20 °C. Natural lighting was supported by artificial light and deionized water was used to regulate soil moisture. Forage was harvested and the plants fertilised three times during the basic experiment, followed by an extra fertilisations and harvests. At the end of the experiment CH₄ production and CH₄ oxidation potentials were determined; roots were collected and the biomass was determined. From the three first harvests the amount of total N in the aboveground biomass was determined. N₂O and CH₄ exchange was monitored using a closed chamber technique and a gas chromatograph. The highest N₂O fluxes (on average, 255 μg N₂O m⁻² h⁻¹ during period IV) occurred just after fertilisation at high water contents, and especially at the beginning of the growing season (on average, 490 μg N₂O m⁻² h⁻¹ during period I) when the competition of vegetation for N was low. CH₄ fluxes were negligible throughout the experiment, and for all treatments the production and oxidation potentials of CH₄ were inconsequential. Especially at the highest rates of fertilisation, the elevated supply of CO₂ increased above- and below-ground biomass production, but both at the highest and lowest rates of fertilisation, decreased the total amount of N in the aboveground dry biomass. N₂O fluxes tended to be higher under doubled CO₂ concentrations, indicating that increasing atmospheric CO₂ concentration may affect N and C dynamics in farmed peat soil.     

Elevated CO2 stimulates N2O emissions in permanent grassland

To evaluate climate forcing under increasing atmospheric CO₂ concentrations, feedback effects on greenhouse gases such as nitrous oxide (N₂O) with a high global warming potential should be taken into account. This requires long-term N₂O flux measurements because responses to elevated CO₂ may vary throughout annual courses. Here, we present an almost 9 year long continuous N₂O flux data set from a free air carbon dioxide enrichment (FACE) study on an old, N-limited temperate grassland. Prior to the FACE start, N₂O emissions were not different between plots that were later under ambient (A) and elevated (E) CO₂ treatments, respectively. However, over the entire experimental period (May 1998–December 2006), N₂O emissions more than doubled under elevated CO₂ (0.90 vs. 2.07 kg N₂O-N ha⁻¹ y⁻¹ under A and E, respectively). The strongest stimulation occurred during vegetative growth periods in the summer when soil mineral N concentrations were low. This was surprising because based on literature we had expected the highest stimulation of N₂O emissions due to elevated CO₂ when mineral N concentrations were above background values (e.g. shortly after N application in spring). N₂O emissions under elevated CO₂ were moderately stimulated during late autumn–winter, including freeze–thaw cycles which occurred in the 8th winter of the experiment. Averaged over the entire experiment, the additional N₂O emissions caused by elevated CO₂ equaled 4738 kg CO₂-equivalents ha⁻¹, corresponding to more than half a ton (546 kg) of CO₂ ha⁻¹ which has to be sequestered annually to balance the CO₂-induced N₂O emissions. Without a concomitant increase in C sequestration under rising atmospheric CO₂ concentrations, temperate grasslands may be converted into greenhouse gas sources by a positive feedback on N₂O emissions. Our results underline the need to include continuous N₂O flux measurements in ecosystem-scale CO₂ enrichment experiments.     

Relationship between soil CO2 concentrations and forest-floor CO2 effluxes

To better understand the biotic and abiotic factors that control soil CO₂ efflux, we compared seasonal and diurnal variations in simultaneously measured forest-floor CO₂ effluxes and soil CO₂ concentration profiles in a 54-year-old Douglas fir forest on the east coast of Vancouver Island. We used small solid-state infrared CO₂ sensors for long-term continuous real-time measurement of CO₂ concentrations at different depths, and measured half-hourly soil CO₂ effluxes with an automated non-steady-state chamber. We describe a simple steady-state method to measure CO₂ diffusivity in undisturbed soil cores. The method accounts for the CO₂ production in the soil and uses an analytical solution to the diffusion equation. The diffusivity was related to air-filled porosity by a power law function, which was independent of soil depth. CO₂ concentration at all depths increased with increase in soil temperature, likely due to a rise in CO₂ production, and with increase in soil water content due to decreased diffusivity or increased CO₂ production or both. It also increased with soil depth reaching almost 10 mmol mol⁻¹ at the 50-cm depth. Annually, soil CO₂ efflux was best described by an exponential function of soil temperature at the 5-cm depth, with the reference efflux at 10 °C (F₁₀) of 2.6 μmol m⁻² s⁻¹ and the Q₁₀ of 3.7. No evidence of displacement of CO₂-rich soil air with rain was observed.Effluxes calculated from soil CO₂ concentration gradients near the surface closely agreed with the measured effluxes. Calculations indicated that more than 75% of the soil CO₂ efflux originated in the top 20 cm soil. Calculated CO₂ production varied with soil temperature, soil water content and season, and when scaled to 10 °C also showed some diurnal variation. Soil CO₂ efflux and concentrations as well as soil temperature at the 5-cm depth varied in phase. Changes in CO₂ storage in the 0–50 cm soil layer were an order of magnitude smaller than measured effluxes. Soil CO₂ efflux was proportional to CO₂ concentration at the 50-cm depth with the slope determined by soil water content, which was consistent with a simple steady-state analytical model of diffusive transport of CO₂ in the soil. The latter proved successful in calculating effluxes during 2004.     

外源H2O2对镉胁迫下酸枣幼苗生长及生理特性的缓解效应

通过温室盆栽土培试验,研究不同浓度(0,0.02,0.04,0.06,0.08,0.1,0.3 mmol/L)的外源H_2O_2处理对0.05 mmol/L Cd胁迫下酸枣幼苗生长、光合系统和荧光特性等的影响。结果表明:(1)Cd胁迫下,酸枣幼苗生长受到抑制,经H_2O_2处理后,酸枣幼苗对镉抗性系数、光合绿素含量、净光合速率(P_n)、蒸腾速率(T_r)和气孔导度(G_s)均升高,过氧化氢(H_2O_2)、丙二醛(MDA)含量和胞间CO_2浓度(C_i)则出现不同程度的下降;(2)低浓度H_2O_2(≤0.08 mmol/L)处理后,酸枣叶片和根系内抗氧化酶[过氧化物酶(POD)、超氧化物歧化酶(SOD)、过氧化氢酶(CAT)]活性增强,叶片内1,5—二磷酸核酮糖羧化酶(Rubisco)、1,1—二磷酸景天庚酮糖酯酶(SBPase)和1,6—二磷酸果糖醛缩酶(FBAase)活性最高显著上升38.24%,42.15%,84.08%,但转酮醇酶(TKase)活性无显著变化;(3)酸枣叶片内PSⅡ最大光化学效率(F_v/F_m)、实际光化学效率(ΦPSⅡ)、光化学猝灭系数(qP)和吸收光能用于光化学反应的份额(P)在H_2O_2处理下最大分别提高37.52%,135.95%,53.10%和98.36%,PSⅡ非光化学猝灭系数(NPQ)、调节性能量耗散Y(NPQ)、非调节性能量耗散Y(NO)、吸收光能用于天线热耗散的份额(D)、PSⅡ反应中心非光化学耗散的份额(E_x)和双光系统间激发能分配不平衡偏离系数(β/α-1)分别降低34.13%,35.15%,30.26%,35.52,32.30%和53.43%,缓解效果显著,但随着外源H_2O_2喷施浓度的增加,缓解效应有下降趋势。综合分析发现,H_2O_2对酸枣镉毒的缓解作用与其改善酸枣光合作用、维持抗氧化系统高活性和提高PSⅡ光化学效率等多种生理过程有关。其中以0.08 mmol/L H_2O_2提高酸枣的修复效率最佳,可作为植物修复的强化措施。