Phosphonate‐Modified UiO‐66 Brønsted Acid Catalyst and Its Use in Dehydra‐Decyclization of 2‐Methyltetrahydrofuran to Pentadienes

Phosphorus‐modified all‐silica zeolites exhibit activity and selectivity in certain Brønsted acid catalyzed reactions for biomass conversion. In an effort to achieve similar performance with catalysts having well‐defined sites, we report the incorporation of Brønsted acidity to metal–organic frameworks with the UiO‐66 topology, achieved by attaching phosphonic acid to the 1,4‐benzenedicarboxylate ligand and using it to form UiO‐66‐PO₃H₂ by post‐synthesis modification. Characterization reveals that UiO‐66‐PO₃H₂ retains stability similar to UiO‐66, and exhibits weak Brønsted acidity, as demonstrated by titrations, alcohol dehydration, and dehydra‐decyclization of 2‐methyltetrahydrofuran (2‐MTHF). For the later reaction, the reported catalyst exhibits site‐time yields and selectivity approaching that of phosphoric acid on all‐silica zeolites. Using solid‐state NMR and deprotonation energy calculations, the chemical environments of P and the corresponding acidities are determined.     

Combined Intrinsic and Extrinsic Proton Conduction in Robust Covalent Organic Frameworks for Hydrogen Fuel Cell Applications

Developing new materials for the fabrication of proton exchange membranes (PEMs) for fuel cells is of great significance. Herein, a series of highly crystalline, porous, and stable new covalent organic frameworks (COFs) have been developed by a stepwise synthesis strategy. The synthesized COFs exhibit high hydrophilicity and excellent stability in strong acid or base (e.g., 12 m NaOH or HCl) and boiling water. These features make them ideal platforms for proton conduction applications. Upon loading with H₃PO₄, the COFs (H₃PO₄@COFs) realize an ultrahigh proton conductivity of 1.13×10^?1 S cm^?1, the highest among all COF materials, and maintain high proton conductivity across a wide relative humidity (40–100 %) and temperature range (20–80 °C). Furthermore, membrane electrode assemblies were fabricated using H₃PO₄@COFs as the solid electrolyte membrane for proton exchange resulting in a maximum power density of 81 mW cm^?2 and a maximum current density of 456 mA cm^?2, which exceeds all previously reported COF materials.     

Improving the Yield and Rate of Acid-Catalyzed Deconstruction of Lignin by Mechanochemical Activation

Lignin is a potential biomass feedstock from plant material, but it is particularly difficult to economically process. Inspired by recent ball-milling results, state-of-the-art quantum mechanochemistry calculations have been performed to isolate and probe the purely mechanochemical stretching effect alone upon acid-catalyzed deconstruction of lignin. Effects upon cleavage of several exemplary simple ethers are examined first, and with low stretching force they all are predicted to cleave substantially faster, allowing for use of milder acids and lower temperatures. Effects upon an experimentally known lignin fragment model (containing the ubiquitous β-O-4 linkage) are next examined; this first required a mechanism refinement (3-step indirect cleavage, 1-step side reaction) and identification of the rate-limiting step under zero-force (thermal) conditions. Mechanochemical activation using very low stretching forces improves at first only yield, by fully shutting off the ring-closure side reaction. At only somewhat larger forces, in stark contrast, a switch in mechanism is found to occur, from 3-step indirect cleavage to the direct cleavage mechanism of simple ethers, finally strongly enhancing the cleavage rate of lignin. It is concluded that mechanochemical activation of the common β-O-4 link in lignin would improve the rate of its acidolysis via a mechanism switch past a low force threshold. Relevance to ball-milling experiments is discussed.     

回流式无级变速传动系统效率优化匹配策略

针对回流式无级变速传动系统效率变化幅度大,传统无级变速系统匹配控制策略无法确保整个系统处于理想状态,提出了基于系统效率优化的匹配控制策略。建立了发动机、变速器效率数值模型和整车优化模型,利用Matlab/Simulink仿真平台,对优化模型进行求解,得到了发动机目标节气门开度控制表和变速器目标速比控制表,对设计样车的燃油经济性进行了欧洲市区与城郊行驶循环(ECE+EUDC)工况仿真验算,结果表明:基于系统效率优化的匹配控制策略可提高整车燃油经济性1.5%左右。     

中国沙棘平茬萌蘖种群的生物量动态

 平茬萌蘖是中国沙棘种群更新的有效方式,但其中的生态学机制并不清楚,为此,以样地每木检尺资料为基础,以 "空间差异代替时间变化法"及"样地编年序列法"原理为依据、以生物量投资与分配为指标,探讨了中国沙棘平茬更新的生态学机制.结果表明:① 中国沙棘平茬萌蘖种群及其构件生物量积累过程均符合Logistic方程,可分为慢、快、慢3个阶段,但构件之间的生物量投资与分配具有明显差异;② 通过构件之间的生物量投资与分配调节,中国沙棘实现了平茬后的萌蘖更新,尤其是萌蘖根的生物量投资具有"前置效应"和"主导效应";③ 地上与地下构件的生物量分配具有互补效应,即地下分配比例大时则地上分配比例小.因此,种群实施萌蘖更新过程中,必须在繁殖与生长之间做出权衡.     

西双版纳地区橡胶林生物量的遥感估算

以西双版纳地区橡胶林为对象,设置93个900 m2样地并测量每株胸径等数据,根据经验式计算样地生物量,并分析了生物量与样地调查时间接近的2010年Landsat TM影像的反射率和植被指数的相关性,建立生物量估算模型,计算了该地区橡胶林生物量.结果表明:①生物量与可见光波段(TM1,TM2,TM3)(P<0.01)和中红外波段(TM5,TM7)反射率呈显著负相关(P<0.05),与NDVI,RVI和GI植被指数则呈显著正相关(P<0.01);②GI植被指数是生物量的最佳估算因子;③橡胶林生物量变化在1～291 t.hm-2之间,平均值为(75.90±58.75)t.hm-2,总生物量为1.97×107 t;④生物量在景洪市和勐腊县南部地区较高,且随海拔升高呈现出先增加后减少趋势,最大值出现在600～700 m.     

云黄连不同部位生物量及生物碱含量个体差异初探

以道地产区3个不同居群云黄连为研究材料,对不同单株不同部位(根茎、须根、叶)生物量及主要生物碱(小檗碱、药根碱、巴马汀)含量进行比较分析.结果表明:3个不同居群单株生物量及生物碱含量均存在较大个体差异,其中,单株根茎最稳定,叶次之,须根个体差异最大;作为非传统用药部位的叶和须根中的主要生物碱总量约占整株中将近1/3,可...     

1 kW自呼吸PEMFC堆控制因素试验

自呼吸质子交换膜燃料电池(PEMFC)阴极侧湿度和温度耦合严重,且空气流量对湿度和温度影响不同,从而使得对电池输出电压的控制变得复杂.以氢气压力和提供阴极空气流量的风扇转速为影响因素,对相应的工作点集进行了正交试验研究.分析结果表明,风扇转速高于极值电压转速时,空气会带走更多的水分,从而使得质子交换膜逐渐干燥,阻抗增大,电池性能衰减;风扇转速低于极值电压转速时,空气流量带走的热量减少,使得阴极表面温度升高,阴极端相对湿度迅速减低,从而导致质子交换膜迅速干燥,电池性能衰减迅速.因此,每个工作点存在一个使电池电压最高的风扇转速值.     

模拟酸雨对土荆芥生长和抗氧化酶活性的影响

以入侵植物土荆芥为研究材料,同属植物藜作为对照,研究在不同pH值的模拟酸雨处理下,土荆芥生长及抗氧化酶活性的变化.结果表明:土荆芥根受到的影响最为严重,根质量比和根冠比随模拟酸雨pH值的减小显著下降,而叶和茎受到的影响不大.随着模拟酸雨胁迫程度的加深,SOD活性呈上升趋势,CAT活性呈下降趋势,POD活性则表现为先升后降,呈单峰曲线型变化.藜的生长变化与土荆芥相似;而酶活性中,SOD活性变化与土荆芥一致,CAT和POD活性均具有不同的变化趋势.藜对当地的酸雨已具有一定的适应性,但强酸雨条件下土荆芥比藜具有更高的适应能力.