不同温度下水稻秸秆多孔生物炭结构与电化学性能

针对一步热解活化技术制备的秸秆多孔生物炭的表面活性位点偏少、孔隙结构不发达和电化学性能欠佳的问题,该研究以水稻秸秆微波磷酸水热炭为前驱体,开展500～900 ℃下多孔生物炭的制备试验,探讨不同温度下多孔生物炭的结构及电化学性能。结果表明,随着活化温度的升高,水稻秸秆多孔生物炭产率由50.31%降低到33.47%,800 ℃多孔生物炭的C含量最高,为74.09%。多孔生物炭表面上含有的-OH、C-O-C等含O基团和吡啶氮、吡咯氮、石墨氮和氮的氧化物等含N基团,有利于其在电解质中的润湿性,降低离子转移电阻。随着活化温度的升高,多孔生物炭的碳的无序度和缺陷程度先增加后降低。800 ℃多孔生物炭的表面缺陷较多,其比表面积为1 002.20 m2/g,总孔体积最大为0.79 cm3/g,中孔体积率为45.57%。在三电极的KOH电解质体系下,800 ℃多孔生物炭电极的比电容最大,倍率性能较好,电阻较小,且其在1 A/g电流密度下的比电容为312.81 F/g。800 ℃多孔生物炭制备的对称电容器在228 W/kg功率密度下的能量密度达到10.73 W·h/kg,且在10 A/g电流密度和5 000次循环充放电后,其比电容保持率为95.82%。     

稳定农作物生长环境温度的相变储能材料制备与性能

为了稳定农作物适宜生长的环境温度,该研究从微封装角度开发适用于农业应用的相变微胶囊储能材料,以农作物适宜生长温度（30 ℃左右）为基础制备TiO₂@正十八烷微胶囊（相变温度25～33 ℃）,并通过氧化石墨烯（GO）对微胶囊的热性能进行修饰优化处理获得GO/TiO₂@正十八烷微胶囊。在此基础上,针对所制备的GO/TiO₂@正十八烷微胶囊测定了其样品的形貌、化学组成,最后对样品的热物性进行了检测分析。结果表明：所制备的微胶囊在扫描电镜观测下呈球形,平均直径1～3μm,颗粒均匀,且具有完整的核壳结构,还可观察到纳米GO片附着在微胶囊表面;红外测试结果表明GO与微胶囊并未发生化学反应,两者属于物理结合;试验所制备的储能微胶囊的包封率约为52.9 %,利用质量分数为1 %、2 %、3 %GO修饰后微胶囊包封率分别为43.3 %、41.2 %、37.6 %,差示扫描量热仪测试数据表明TiO₂@正十八烷微胶囊的熔融焓和结晶焓分别为120、116 J/g;采用质量分数为1 %、2 %、3 %的GO对所制备的TiO₂@正十八烷微胶囊进行修饰后,其热导率相比未经GO修饰微胶囊分别提升了57.5 %、86.3 %、104.2 %。最后,综合差示扫描量热(Differential scanning calorimetry)测试和热重分析测试数据可知该研究方法所制备的GO/TiO₂@正十八烷微胶囊具有较为理想的相变潜热和高导热性能的特性,同时其具有良好的热稳定性和使用寿命,应用前景广泛,可为低温能源的二次利用提供一种新的参考方案。     

微藻油脂制备生物基多元醇理化性能分析与结构表征

为了实现有效高值利用非食用、不占耕地的绿色可再生油脂资源,该研究以微藻油脂为原料,采用环氧化-开环法和氢甲酰化-加氢还原法制备了2种生物基多元醇,通过主要理化指标碘值、酸值、环氧基含量、羟值的测定,重要理论理化指标理论双键含量、理论环氧基含量、理论羟值、转化率和选择性的计算,结合气质联用、凝胶渗透色谱、红外光谱、核磁共振等仪器分析手段,对原料和产物的理化性能和结构进行分析与表征。结果表明,微藻油脂的主要脂肪酸是油酸,质量分数为91.10%,碘值为88.46 g/100 g,理论双键含量0.34 mol/100 g,环氧-开环法得到的多元醇碘值降至0.62 g/100 g,羟值为150.35 mg/g,原料转化率和目标产物选择性分别为99.30%和86.74%,结构中引入仲羟基,通过及时除去环氧反应过程中生成的水、开环反应选择适宜的醇用量可提升产品质量。氢甲酰化-加氢还原法得到的多元醇碘值降至2.12 g/100 g,羟值为166.29 mg/g,原料转化率和目标产物选择性分别为97.60%和95.83%,结构中引入伯羟基,该法为非均相反应,催化剂过滤可除,副反应少,溶剂廉价可回收,产品...     

棉秆与污泥共热解制备生物炭工艺优化及其结构与吸附性能

随着经济的发展,产量巨大的棉秆与污泥亟需找到新的资源化方式。该研究利用污泥与棉秆共热解制备炭,采用正交试验法全面考察与分析了各因素对污泥-棉秆炭吸附性能以及表面结构的影响。结果表明,污泥质量分数、KOH浓度、微波功率、辐照时间以及装填量均会显著影响污泥-棉秆炭的吸附性能、表面官能团以及孔结构。优化工艺参数为:污泥质量分数30%,微波功率280 W,辐照时间24 min,KOH质量分数50%,装填量150 g,在该工艺条件可制备获得综合吸附性能较优的污泥-棉秆炭,其亚甲基蓝、酸性品红、硫酸铜以及碘的吸附值分别达到157.80、293.39、272.12、1 281.93 mg/g。污泥-棉秆炭的吸附性能可达到或超过国家木质净水用活性炭一级品的标准,但吸附质与炭的结构特性均会影响其吸附性能。酸性官能团总量与孔容分别与酸性品红吸附值及硫酸铜吸附值显著相关,其他结构参数与吸附性能相关性不显著,污泥-棉秆炭对污染物的吸附并不只是单一的物理吸附或化学吸附。该研究结果对于定向设计高效的棉秆-污泥炭基吸附剂具有参考价值。     

秸秆微波水热炭和活性炭理化及电化学特性

为了解秸秆微波酸催化水热炭和碱活化活性炭形成机制和理化特性演变规律,该研究开展了不同柠檬酸质量分数下的秸秆微波水热和活性炭的制备试验,并研究了水热炭和活性炭理化及其电化学特性。结果表明,随柠檬酸质量分数的增加,秸秆水热炭的产率、挥发份和H含量减少,而其灰分、固定碳、C和高位热值增加,且酸质量分数为10%后趋于稳定。柠檬酸质量分数为10%时,水热炭的碳微球结构最丰富,其比表面积和孔体积最大,且以中孔为主。10%柠檬酸水热炭在900℃下经KOH活化后的活性炭产率为8%～11%,活化气体产率为32%～35%,且以CO和H2为主。900 ℃活性炭的比表面积为1 250～1 570 m2/g,总孔体积为1.00～1.20 cm3/g,孔径为3.55～4.10 nm,且以中孔和微孔为主。当电流密度为1 A/g,水稻、玉米和油菜秸秆活性炭的比电容分别为160.54、150.12和155.17 F/g,且循环5 000次后的电容保持率分别为91.04%、88.12%和89.06%,表现出较好的循环稳定性。水稻秸秆水热炭和活性炭的产率、灰分、碳转化率、能量转化率、比表面积、总孔体积、比电容和电容保持率最大。     

文冠果壳基活性炭制备工艺优化与性能表征

文冠果壳为文冠果榨油后的废弃物,为避免环境污染,充分利用这种废弃物制成高附加值的活性炭,该研究以文冠果壳为原料,采用磷酸活化法制备活性炭,以固液比、磷酸浓度、活化时间和活化温度为自变量,活性炭的碘吸附值为因变量,经响应面试验优化制备工艺,探究文冠果壳活性炭的吸附性能。结果表明,通过响应面试验优化得到最佳工艺条件：固液比1∶1 g/mL,磷酸浓度71%,活化时间158 min,活化温度540℃,此时碘吸附值为(1 127.377±2.406) mg/g,与预测的碘吸附值误差仅为0.390%。与文冠果壳相比,经活化得到的活性炭水分和灰分明显降低,C元素质量分数升高至69.702%;活性炭的比表面积为841.438 m²/g,总孔容为0.593 cm³/g,平均孔径为4.361 nm,孔隙结构发达,主要以介孔为主,且官能团主要为羰基。因此可以用文冠果壳制备出吸附性能好的活性炭,该结果可为磷酸活化法制备文冠果壳基活性炭的工业化生产提供一定参考。     

氮磷硫共掺杂生物质基多孔炭的制备及其电化学性能

为了提升农林废弃物在储能领域的高附加值利用,该研究以杉木屑为原料,磷酸三聚氰胺为磷、氮源,基于冷冻NaOH/硫脲体系溶解木质原料中纤维素,通过一步热解制备氮、磷、硫共掺杂多孔炭,并考察活化温度、NaOH/杉木屑质量比和冷冻条件对多孔炭结构及电化学性能的影响。通过X射线光电子能谱（XPS, X-ray photoelectron spectroscop ）和比表面积分析仪（BET,Brunauer-Emmett-Teller）研究多孔炭的表面结构和孔隙结构;采用循环伏安（CV,cyclic voltammetry）、恒流充放电（GCD,galvanostatic charge/discharge）和交流阻抗（EIS,electrochemical impedance spectroscopy）等测试手段表征其电化学性能。研究结果表明：随着活化温度和NaOH/杉木屑质量比的增加,多孔炭的表面积、全孔孔容和比电容呈现先增加后减小的趋势;冷冻条件和磷酸三聚氰胺的加入可以增加多孔炭的比表面积和全孔孔容,提升电化学性能。当活化温度900 ℃,NaOH/杉木屑质量比为1.2时,制备的氮、磷、硫共掺杂多孔炭的比表面积为2 048 m²/g,全孔孔容为1.655 cm³/g,介孔率为99.7%,氮、磷、硫的含量为3.41%、0.29%、1.40%。三电极体系下、6 mol/L KOH电解液中,当电流密度0.5 A/g时,比电容可达261 F/g。用NPS-900-1.2组装的对称超级电容器5 A/g电流密度条件下,比电容值为108 F/g,循环5 000次后库伦效率接近100%,电容保持率为92%。对称的超级电容器功率密度为248 W/kg时,能量密度可达17.2 Wh/kg。该研究为农林废弃物制备高性能超级电容器提供了参考依据。     

Fate of nitrogen and carbon in the vadose zone: in situ and laboratory measurements of seasonal variations in aerobic respiratory and denitrifying activities

In situ and laboratory measurements of aerobic respiratory and denitrifying activities were studied in the vadose zone (almost 2.5 m thick) of a fluvic hypercalcaric cambisol characterized by transitory anaerobic conditions. A field experiment was conducted in a bare soil, over a 7-month period starting just after maize harvest and incorporation of maize crop residues. Weather variables (air and soil temperature, rainfall), soil water content, soil solutes (NO₃⁻ and dissolved organic carbon) and soil gases (CO₂ and N₂O), were recorded throughout the experiment. Four soil layers were defined. Bacterial counts were performed in each layer using the most probable number (MPN) method. Aerobic respiratory and denitrifying activities were estimated from laboratory measurements. In situ microbial activity, as revealed by CO₂ and N₂O measurements in the soil atmosphere, was strongly influenced by weather. Laboratory measurements showed that potential aerobic respiratory activity (ARA) occurred throughout the soil profile, whereas semi-potential denitrifying activities SPDA (i.e. measured under organic-C limiting condition) occurred mainly in the top 30 cm soil layer. In the soil profile, the CO₂ concentration gradient was stronger than the N₂O concentration gradient. Seasonal variations in microbial activities increased with depth, whereas DOC concentrations, and variations in those concentrations, decreased with depth, suggesting that DOC quality investigations are necessary in the deep vadose zone to understand microbial activities seasonal variations. Laboratory measurements of potential activities agreed well with in situ microbial activity in natural environmental conditions. NO₃⁻ was a stronger limiting factor for SPDA than was denitrifier density in the soil profile.     

Comparison of the effects of nano-iron fertilizer with iron-chelate on growth parameters and some biochemical properties of Catharanthus roseus

Nanofertilizers, which supply nutrients to the plant, are used to replace conventional fertilizers. Iron (Fe) is one of the essential elements for plant growth and plays an important role in the photosynthetic reactions. To study the effects of nano-iron fertilizer on Catharanthus roseus, plants were treated with different concentrations (0, 5 10 20, 30, and 40 mM) of iron oxide nanoparticles (Fe2O3) for 70 days. Fe₂O₃ nanoparticles increased growth parameters, photosynthetic pigments, and total protein contents in the treated plants significantly. The maximum amounts of growth parameters, photosynthetic pigments, and protein contents were obtained with 30 µM Fe₂O₃ and minimum values of these parameters were found with 0 µM Fe₂O₃. The highest value of total alkaloid content was obtained in 0 µM Fe₂O₃ and the lowest value was observed in control plants. Iron oxide nanoparticles increased potassium, phosphorus, and iron absorption but did not show a significant effect on sodium content.     

氧化还原类酶活性在农业废弃物静态高温堆腐过程中变化的研究

以鸡粪和麦秸为原料,在静态通气条件下,研究了堆腐过程堆体温度及氧化还原酶活性变化。结果表明,添加微生物菌剂后,堆体不同部位温度均高于CK(不加微生物菌剂)处理,且升温阶段持续时间较短。微生物菌剂处理堆料50℃以上的持续时间为14～20 d,CK处理50℃以上的持续时间7.5～10 d;添加微生物菌剂处理的过氧化氢酶活性在第1～26 d均大于CK处理;堆料中添加菌剂处理在堆腐中期的脱氢酶活性大于CK处理;添加菌剂处理在堆肥的第5～28 d,多酚氧化酶活性大于CK处理的活性;说明微生物菌剂可促进有机物的降解及其降解产物的转化。添加菌剂处理在堆腐30 d后E₄/E₆(为胡敏酸在465 nm与665 nm波长下吸光值的比值)比值为1.57～1.68,CK处理为2.16～2.41,表明添加菌剂能促进腐殖质的缩合和芳构化。     

Effect of CO2 enrichment on carbon and nitrogen interaction in wheat and soybean

Effect of CO₂ enrichment on the carbon-nitrogen balance in whole plant and the acclimation of photosynthesis was studied in wheat (spring wheat) and soybean (A62-1 [nodulated] and A62-2 [non-nodulated]) with a combination of two nitrogen application rates (0 g N land area m^-2 and 30 g N land area m^-2) and two temperature treatments (30/20°C (day/night) and 26/16°C). Results were as follows.

1. Carbon (dry matter)-nitrogen balance of whole plant throughout growth was remarkably different between wheat and soybean, as follows: 1) in wheat, the relationship between the amount of dry matter (DMt) and amount of nitrogen absorbed (Nt) in whole plant was expressed by an exponential regression, in which the regression coefficient was affected by only the nitrogen application rate, and not by CO₂ and temperature treatments, and 2) in soybean the DMt-Nt relationship was basically expressed by a linear regression, in which the regression coefficient was only slightly affected by the nitrogen treatment (at 0N, DMt-Nt balance finally converged to a linear regression). Thus, carbon-nitrogen interaction in wheat was strongly affected by the underground environment (nitrogen nutrition), but not by the above ground environment (CO₂ enrichment and temperature), while that in soybean was less affected by both under and above ground environments.

2. The photosynthetic response curve to CO₂ concentration in wheat and soybean was less affected by the CO₂ enrichment treatment, while that in wheat and soybean (A62-2) was affected by the nitrogen treatment, indicating that nitrogen nutrition is a more important factor for the regulation of photosynthesis regardless of the CO₂ enrichment.

3. Carbon isotope discrimination (..:1) in soybean was similar to that in wheat under ambient CO₂, while lower than that in wheat under CO₂ enrichment, suggesting that the carbon metabolism is considerably different between wheat and soybean under the CO₂ enrichment conditions.     

Microbial activity and bacterial composition of H2-treated soils with net CO2 fixation

The effects of H₂ gas treatment of an agricultural soil cultivated previously with a mixture of clover (Trifolium pratense) and alfalfa (Medicago sativa) on CO₂ dynamics and microbial activity and composition were analyzed. The H₂ emission rate of 250 nmol H₂ g⁻¹ soil h⁻¹ was similar to the upper limit of estimated H₂ amounts emitted from N₂ fixing nodules into the surrounding soil ([Dong, Z., Layzell, D.B., 2001. H₂ oxidation, O₂ uptake and CO₂ fixation in hydrogen treated soil. Plant and Soil 229, 1-12.]). After 1 week of H₂ supply to soil samples simultaneously with H₂ uptake net CO₂ production declined continuously and this finally led to a net CO₂ fixation rate in the H₂-treated soil of 8 nmol CO₂ g⁻¹ soil h⁻¹. The time course of H₂ uptake and CO₂ fixation in the soils corresponded with an increase in microbial activity and biomass of the H₂-treated soil determined by microcalorimetric measurements, fluorescence in situ hybridization analysis (FISH) and DNA staining (DAPI). Shifts in the bacterial community structure caused by the supply of H₂ were recorded. While the H₂ treatment stimulated β-and γ-subclasses of Proteobacteria, it had no significant effect on α-Proteobacteria. In addition, FISH-detectable bacteria of the Cytophaga-Flavobacterium-Bacteroides phylum increased in numbers.     

不同水分条件下CO2浓度升高对冬小麦碳氮转运的影响

CO2浓度升高对作物的影响日益受到重视,水分是作物生长的必要条件之一。冬小麦是我国的主要粮食作物之一,阐明高CO2浓度和水分条件互作对冬小麦碳氮转运的影响,对客观认识气候变化背景下作物的水分管理及肥料施用具有实际指导意义。本研究利用开放式CO2富集系统(FACE)平台,以冬麦品种‘中麦175’为试验材料,采用盆栽试验方法,研究了不同CO2浓度[正常浓度(391±40)μmol·mol?1和高浓度(550±60)μmol·mol?1]及水分条件(湿润条件和干旱条件,即75%和55%田间土壤最大持水量)的冬小麦花前碳氮积累及花后碳氮转运的规律特征。结果表明:湿润条件下,与正常CO2浓度相比,高CO2浓度促进冬小麦地上部干物质及碳氮积累,开花期增幅分别为18.1%、16.5%、14.9%,成熟期增幅分别为6.6%、1.3%、4.5%,并提高碳氮转运能力及对籽粒贡献率,转运量、转运率及对籽粒贡献率的增幅碳素依次为39.3%、20.0%、30.0%,氮素依次为19.1%、3.8%、10.8%。干旱条件下,与正常CO2浓度相比,高CO2浓度对地上部碳氮积累有一定的促进作用,开花期和成熟期碳积累量分别增加3.0%和10.7%,氮积累量分别增加0和15.8%;但高CO2浓度阻碍了碳氮的转运,转运量、转运率降幅碳素分别为10.2%、12.8%,氮素分别为7.2%、7.1%;碳氮对籽粒贡献率则变化不同,碳降低14.4%,而氮升高31.3%。干旱及高CO2浓度互作与湿润条件正常CO2浓度处理相比,冬小麦碳素转运对籽粒贡献率降低更明显,地上部碳素转运量、转运率及对籽粒贡献率降幅分别为36.2%、16.9%、22.3%,但提高了氮素转运对籽粒贡献率,氮素转运量及转运率分别降低35.7%、15.2%,对籽粒贡献率增加7.0%。综合而言,高CO2浓度可促进冬小麦碳氮积累及其在花后向籽粒的转运,水分不足可能成为主要的物质转运障碍因子,限制CO2促进作用发挥。