Highly selective synthesis for 4,4′-bisphenol F from phenol and formaldehyde catalyzed with [C_4mim][HSO_4] ionic liquid

The effects of N-methylimidazole cation [Cnmim] with different alkyl chain lengths, the types of cations and anions of ionic liquids and the reaction parameters on the catalytic activity and the selectivity for 4,4′-bisphenol F were investigated. The hydrogen bonding between the hydroxyl of phenol and the C2-position hydrogen of imidazole moiety in hydrophilic imidazole-based ionic liquid has important influence on the selectivity for 4,4′-bisphenol F, and under the conditions of the molar ratio of phenol/[C4mim][HSO4] 1:1, reaction temperature65 °C and the theoretical molar ratio of phenol/formaldehyde 2:1, the selectivity for 4,4′-bisphenol F reached69.1%. Compared with the high phenol/formaldehyde ratio reported in literatures, the low molar ratio of phenol/formaldehyde and the low reaction temperature can greatly reduce energy consumption, and has important significance for industrial application.

Drought changes and the mechanism analysis for the North American Prairie

The worst droughts in the central part of the North American Prairie in the past several hundred years have been reconstructed from tree-ring chronologies, suggesting that some drought years have exceeded the se- verity shown by the gauge record. A general circulation model of the Geophysical Fluid Dynamics Laboratory （GFDL） has simulated climate changes for the area during the past 250 years driven by c^imatic forces, providing scenarios of extreme climate that can further diagnose the mechanisms. This study refined the drought signals from the tree ring data and GFDL modeling at inter-annual and decadal time scales and analyzed the potential mecha- nisms driving the droughts. Results showed that drought years with summer precipitation Ilower than the 10th per- centiles occurred during 1777-1789, 1847-1861 and 1886-1879 AD in the area. Both tree rings and model re- vealed that the frequency of droughts has been relatively consistent in a similar timing andl frequency with climate change. Monte Carlo analysis have detected that the tree ring chronologies have recorded drought years with probabilities of 9.3%-12.8%, and the model has simulated the droughts with probabilities 5..7%-17.8%. Under CO2 and aerosol forcing, the GFDL modeled the drought recurrences of 13 years and 25 years, which are very syn- chronous changes with tree rings and consistent with gauge records. The 20-a and 10-a time scale reoccurrences of droughts are very consistent with solar radiation cycles, and similar to the length of cycles in oceanic records, suggesting that terrestrial precipitation modeling is properly driven from sun-land-sea dynamics. Detected severity, variability and return periods of droughts from the present study make potential improvements in drought predictions and constructing scenarios for climate impacts and adaptation strategies.

Highly spectra-stable pure blue perovskite light-emitting diodes based on copper and potassium co-doped quantum dots

Halide perovskite light emitting diodes(LEDs)have gained great progress in recent years.However,mixed-halide perovskites for blue LEDs usually suffer from electroluminescence(EL)spectra shift at a high applied voltage or current density,limiting their efficiency.In this work,we report a strategy of using single-layer perovskite quantum dots(QDs)film to tackle the electroluminescence spectra shift in pure-blue perovskite LEDs and improve the LED efficiency by co-doping copper and potassium in the mixed-halide perovskite QDs.As a result,we obtained pure-blue halide perovskite QD-LEDs with stable EL spectra centred at 469 nm even at a current density of 1,617 mA·cm^(−2).The optimal device presents a maximum external quantum efficiency(EQE)of 2.0%.The average maximum EQE and luminance of the LEDs are 1.49%and 393 cd·m^(−2),increasing 62%and 66%compared with the control LEDs.Our study provides an effective strategy for achieving spectra-stable and highly efficient pure-blue perovskite LEDs.

Interface-rich Au-doped PdBi alloy nanochains as multifunctional oxygen reduction catalysts boost the power density and durability of a direct methanol fuel cell device

The development of cathode oxygen reduction reaction(ORR)catalysts with high characteristics for practical,direct methanol fuel cells(DMFCs)has continuously increased the attention of researchers.In this work,interface-rich Au-doped PdBi(PdBiAu)branched one-dimensional(1D)alloyed nanochains assembled by sub-6.5 nm particles have been prepared,exhibiting an ORR mass activity(MA)of 6.40 A·mgPd^(−1) and long-term durability of 5,000 cycles in an alkaline medium.The MA of PdBiAu nanochains is 46 times and 80 times higher than that of commercial Pt/C(0.14 A·mgPt^(−1))and Pd/C(0.08 A·mgPd^(−1)).The MA of binary PdBi nanochains also reaches 5.71 A·mgPd^(−1).Notably,the PdBiAu nanochains exhibit high in-situ carbon monoxide poisoning resistance and high methanol tolerance.In actual DMFC device tests,the PdBiAu nanochains enhance power density of 140.1 mW·cm^(−2)(in O_(2))/112.4 mW·cm^(−2)(in air)and durability compared with PdBi nanochains and Pt/C.The analysis of the structure–function relationship indicates that the enhanced performance of PdBiAu nanochains is attributed to integrated functions of surficial defect-rich 1D chain structure,improved charge transfer capability,downshift of the d-band center of Pd,as well as the synergistic effect derived from“Pd-Bi”and/or“Pd-Au”dual active sites.

火山磷供给推动中国北方中生代陆地生物繁荣

中国北方中生代热河生物群的生物量和生物多样性超过了同时期的其他陆地生物群,早白垩世热河生物群的辐射可能是对华北克拉通峰期破坏过程的响应,然而,克拉通破坏的深部过程和陆地生物群演化之间的内在联系尚不清楚。磷是生命所必需的营养元素,火山产物(包括熔岩和火山碎屑岩)中的磷可通过风化作用供给陆地生态系统。中国北方中生代连续的火山-沉积序列记录了火山磷供给、生物生产力和物种丰度的变化,为研究地球深部过程、火山作用与陆地生物群的协同演化提供了关键证据.火山磷供给与生物群演化之间的耦合关系表明,在华北克拉通峰期破坏期间,大量火山产物的风化作用为陆地生态系统供给了丰富的营养物质,创造了有利于热河生物群繁荣的陆地环境。与华北克拉通破坏初期相对应的侏罗纪燕辽生物群的演化也反映了上述火山-生物之间的耦合机制。

基于空心环状CoOOH纳米酶比色检测α-葡萄糖苷酶活性

葡萄糖苷酶是生物体糖代谢途径中不可或缺的一类酶,发展灵敏、便捷的葡萄糖苷酶检测方法对于糖尿病的治疗与预防具有重要意义.本文以空心环状CoOOH纳米酶为探针建立了一种比色检测α-葡萄糖苷酶活性的新方法.研究发现,CoOOH空心纳米环具有优异的类氧化酶活性,能够快速催化溶解氧产生活性氧自由基,从而将无色的底物3,3′,5,5′-四甲基联苯胺(TMB)氧化为蓝色产物oxTMB,并在652 nm处产生较强的特征吸收峰.α-葡萄糖苷酶能水解L-抗坏血酸-2-葡萄糖苷,水解后释放出的抗坏血酸能通过还原作用将CoOOH纳米环转变为无类氧化酶活性的Co^(2+),从而抑制蓝色产物oxTMB的生成.基于该原理,本文建立了一种定量检测α-葡萄糖苷酶活性的新方法,其检测范围为1~40 U/L,检出限为0.1 U/L.该方法具有成本低、操作简单、灵敏度高、选择性好等特点,并可成功用于人血清中α-葡萄糖苷酶活性的测定.

PtCu_(3) nanoalloy@porous PWO_(x) composites with oxygen container function as efficient ORR electrocatalysts advance the power density of room-temperature hydrogen-air fuel cells

It is challenging and desirable to construct Pt-based nanocomposites with oxygen storage function as efficient oxygen reduction reaction(ORR)catalysts for practical proton exchange membrane fuel cells(PEMFCs).Herein,we achieve novel porous nanocomposites of PtCu_(3) nanoalloys-embedded in the PWO_(x) matrix(PtCu_(3)@PWO_(x)),which has an oxygen container feature.The PtCu_(3)@PWO_(x)/C exhibits an ultrahigh mass activity(MA)of 3.94 A·mgPt−1 for ORR,which is 26.3 times as high as the commercial Pt/C and the highest value ever reported for PtCu-based binary system.Theoretical calculations reveal that the compressive strain and d-band center downshift of Pt intrinsically contribute to the excellent ORR performance.In H_(2)-air PEMFCs at room temperature,furthermore,the PtCu_(3)@PWO_(x)/C delivers a high power density(218.6 mW·cm^(−2)),much superior to commercial Pt/C(131.6 mW·cm^(−2)).In H_(2)-O_(2) PEMFCs,PtCu_(3)@PWO_(x)/C outputs a maximum power density of 420.1 mW·cm^(−2).This work provides an effective idea for designing oxygen-storing ORR catalysts used for practical room-temperature H_(2)-air fuel cells.

Low-coordinated surface sites make truncated Pd tetrahedrons as robust ORR electrocatalysts outperforming Pt for DMFC devices

Developing highly stable and active non-Pt oxygen reduction reaction(ORR)electrocatalysts for power generation device raises great concerns and remains a challenge.Here,we report novel truncated Pd tetrahedrons(T-Pd-Ths)enclosed by{111}facets with excellent uniformity,which have both low-coordinated surface sites and distinct lattice distortions that would induce“local strain”.In alkaline electrolyte,the T-Pd-Ths/C achieves remarkable ORR specific/mass activity(SA/MA)of 2.46 mA·cm^(−2)/1.69 A·mgPd^(−1),which is 12.3/16.9 and 10.7/14.1 times higher than commercial Pd/C and Pt/C,respectively.The T-Pd-Ths/C also exhibits high in-situ carbon monoxide(CO)tolerance and 50,000 cycles durability with an activity loss of 7.69%and morphological stability.The rotating ring-disk electrode(RRDE)measurements show that a 4-electron process occurs on T-PdThs/C.Theoretical calculations demonstrate that the low-coordinated surface sites contribute largely to the enhancement of ORR activity.In actual direct methanol fuel cell(DMFC)device,the T-Pd-Ths/C delivers superior open-circuit voltage(OCV)and peak power density(PPD)to commercial Pt/C from 25 to 80℃,and the maximum PPD can reach up to 163.7 mW·cm−2.This study demonstrates that the T-Pd-Ths/C holds promise as alternatives to Pt for ORR in DMFC device.