应用于全固态电池的复合固态电解质的制备实验设计——综合化学实验教学探究

介绍了一种有机-无机复合型固态电解质(SPE)的综合化学实验,使学生了解聚环氧乙烷(PEO)的改性策略及SPE在全固态电池中的应用。通过X射线衍射(XRD)表征晶体结构,采用交流阻抗、线性扫描伏安法、恒流充放电等测试增强学生对极化和离子迁移数等概念的理解。该实验有助于学生将化学中的理论知识延伸至实际运用,提高理论水平,锻炼实践能力。

利用有机超分子光催化剂在太阳光下处理污水的研究进展

对水体中酚类等难降解有机污染物进行深度矿化处理,实现无毒无害排放,是提高环境质量,实现可持续发展的关键.如何高效去除水体中难降解有机污染物不仅是环境化学污染控制的研究热点,也是制约工业废水回用的技术瓶颈.光催化可直接利用太阳光实现污染物的深度矿化和无毒无害排放,为该难题的解决提供了新思路.但对传统无机光催化剂而言,光利用率低、降解速率慢和净化通量低制约了其实际应用.本文总结了本课题组在利用有机光催化剂降解污染物时提出的三个策略,以进一步推动光催化污水处理技术的实际应用.针对可见光利用效率低的难题,发展了一系列有机超分子等新型光催化剂.通过对共轭结构(生色基团)和侧链基团(助色基团)的调控,实现了对最高被占分子轨道(HOMO)和最低未占分子轨道(LUMO)能级位置以及吸光能力的调控,有机半导体光催化剂的降解催化活性可拓展到近红外段,实现了污染物在太阳光下的降解和深度矿化.光生空穴可将酚类和抗生素等难降解污染物完全矿化成CO_(2)和水,建立了可见光下有机半导体光催化剂深度矿化净化水中难降解有机污染物的新方法.通过构建分子内供体受体(DA)结构和分子间供体-受体(D-A)界面,将卟啉和苝二酰亚胺类光催化反应活性拓展到近红外段,太阳光利用效率达70%.针对难降解有机污染物降解去除速率慢的问题,建立了通过光催化剂的分子偶极作用调控内建电场及构建超短迁移路径,进而促进光生电荷的分离和传输,提升污染物降解和矿化动力学.通过支链基团种类和位置调控,发现强极性取代基如羧基、羟基、磺酸基等可以增强偶极作用,而分子偶极在催化剂内有序排列又可以产生强内建电场,从而促进光生电荷的快速分离和迁移到表面,加速污染物的降解反应动力学.通过提升苝二酰亚胺超分子和聚合物光催化剂的结晶度,增强了分子间π–π堆积和氢键的有序度,显著提升了内建电场,实现了光催化氧化反应活性数量级的提高.通过光催化剂尺度和多孔结构调节,电荷迁移距离缩短到纳米和亚纳米量级,增强了电荷迁移到表面的速率.发现并证实了π–π堆积间距的缩短可促进电荷传输,光催化降解活性提高了5–10倍.针对光催化法降解通量低和芬顿法矿化度低的难题,提出了在光催化剂上耦合芬顿催化剂的新思路,创立了光催化原位自芬顿高通量矿化水中有机污染物的新方法.利用光催化的氧化还原反应特性,促进了产双氧水中间体的氧化还原循环,实现了可见光下从纯水到双氧水的高效合成.四羧基卟啉光催化剂产双氧水的活性从可见拓展到1100 nm的红外段,太阳能到双氧水的能量转换效率达1.2%,10 h双氧水积累浓度达到1 wt%,实现了光催化产双氧水性能的新进展.通过在氮化碳光催化剂中引入氧源,使得富氧氮化碳表面生成了大量的酚基和醌基,产双氧水性能可提高3.5倍.通过将g-C_(3)N_(4)、苝-3,4,9,10-四羧酸二亚胺等光催化剂耦合芬顿催化剂,对酚类等难降解污染物的降解活性可提高20倍以上,矿化度提高到90%,解决了传统芬顿法需要外加H_(2)O_(2)的难题.本课题组通过以上三种策略,解决了光催化去除水体污染物过程中太阳光利用率低、矿化度不足和处理通量有限等缺点.未来如何增强超分子光催化剂的稳定性、提高光催化效率以及构建非均相自芬顿体系仍是光催化污水处理技术的研究重点.

基于电诱导沉积原理制备形状可控的海藻酸钙-多聚赖氨酸水凝胶微封装胶囊

海藻酸钙水凝胶是一种具有良好生物相容性、生物降解性的生物医用高分子材料。文中提出了一种基于电诱导沉积原理制备形状可控的海藻酸钙-多聚赖氨酸(PLL)水凝胶微封装胶囊。在涂有光刻胶的FTO导电玻璃表面上利用光刻技术制造多种预设图案的微电极,基于电诱导沉积原理在微电极上制备特定几何结构海藻酸钙水凝胶,通过PLL等试剂的处理最终得到环形与六边形结构的海藻酸钙-PLL水凝胶微封装胶囊,酵母细胞包含在微封装胶囊中进行24 h的培养,获得有一定生物活性的细胞。这种方法可以制备用于组织工程学研究的生物支架,将对细胞装配,生物打印以及药物输送等领域有重要的参考价值。

Mineralogy,geochemistry,and sulfur isotope characteristics of sediment-hosted hydrothermal sulfide minerals from the southern Okinawa Trough

Studies of the mineralogy and sulfur isotope composition of sediment-hosted hydrothermal sulfide minerals in cores are important for understanding the seafloor mineralization environment and material source and reconstructing the hydrothermal history.However,the source of ore-forming materials and the history of hydrothermal activity in the southern Okinawa Trough(SOT)remain unclear.Here,the mineralogy and sulfur isotope characteristics of sulfides from gravity core HOBAB4-S2,collected between the Yonaguni Knoll IV hydrothermal field(HF)and the Tangyin HF,was investigated.Enrichments in Zn(up to 321×10^(-6)),Cu(up to73.7×10^(-6)),and Pb(up to 160×10^(-6))and the presence of pyrite,galena,pyrrhotite and minor sphalerite and chalcopyrite provide evidence for the input of hydrothermal materials into the sediments.The pyrite morphologies include disseminated cubic,pentagonal dodecahedron,and framboidal forms.Except for minor framboidal pyrite,euhedral pyrite from core HOBAB4-S2 is mainly of hydrothermal origin with Co/Ni ratios>1 and S/Fe atomic ratios<2 in the Cu-Zn-Pb-rich layers.The occurrences of hexagonal pyrrhotite,high-Co(up to0.17%)pyrite and high-Fe sphalerite indicate that the hydrothermal precipitates formed at medium-high temperatures and low-sulfur fugacity(f S_(2))environments.The δ^(34) S values of sulfides(0.21‰–3.45‰)with low-f S_(2) mineral assemblages(e.g.,pyrrhotite±high-Fe sphalerite)in the core are significantly lower than those of magmatic rocks and seawater,indicating possible incorporation of previously formed biogenic sulfur in the sediment.Combined with the age model of the core,it is suggested that hydrothermal activity likely began in the Tangyin HF before AD 1445–1483 and that at least three active episodes may have occurred since then.

Fully Printed High‑Performance n‑Type Metal Oxide Thin‑Film Transistors Utilizing Coffee‑Ring Effect

Metal oxide thin-films transistors(TFTs)produced from solution-based printing techniques can lead to large-area electronics with low cost.However,the performance of current printed devices is inferior to those from vacuum-based methods due to poor film uniformity induced by the“coffeering”effect.Here,we report a novel approach to print highperformance indium tin oxide(ITO)-based TFTs and logic inverters by taking advantage of such notorious effect.ITO has high electrical conductivity and is generally used as an electrode material.However,by reducing the film thickness down to nanometers scale,the carrier concentration of ITO can be effectively reduced to enable new applications as active channels in transistors.The ultrathin(~10-nm-thick)ITO film in the center of the coffee-ring worked as semiconducting channels,while the thick ITO ridges(>18-nm-thick)served as the contact electrodes.The fully inkjet-printed ITO TFTs exhibited a high saturation mobility of 34.9 cm2 V^(−1) s^(−1) and a low subthreshold swing of 105 mV dec^(−1).In addition,the devices exhibited excellent electrical stability under positive bias illumination stress(PBIS,ΔV_(th)=0.31 V)and negative bias illuminaiton stress(NBIS,ΔV_(th)=−0.29 V)after 10,000 s voltage bias tests.More remarkably,fully printed n-type metal–oxide–semiconductor(NMOS)inverter based on ITO TFTs exhibited an extremely high gain of 181 at a low-supply voltage of 3 V,promising for advanced electronics applications.

Origin of Cu in the PACMANUS hydrothermal field from the eastern Manus back-arc basin: evidence from mass balance modeling

Hydrothermal precipitates associated with active vents in the eastern Manus Basin, an actively opening back-arc basin in the Bismarck Sea, Papua New Guinea, are among the most Cu-rich on the modern seafloor. The volcanic rocks associated with this mineralization may be insufficiently enriched in Cu to account for the Cu content of the sulfides by simple leaching. The PACMANUS hydrothermal field lies in the eastern portion of the eastern Manus Basin. Mass balance modeling of the PACMANUS hydrothermal system indicates that simple leaching of a stationary reaction zone (0.144 km^3) by hydrothermal fluids cannot yield the Cu found in associated sulfide deposits because unacceptably high leaching, transportation and precipitation efficiencies are required to derive the Cu in sulfides by leaching processes. With 100% leaching, transport and precipitating efficiency, 0.166 km^3 of volcanic rocks would need to be leached to account for the Cu budget of hydrothermal sulfide deposits. The key requirement for forming metal-rich magmatic fluids is a large amount of metals available to enter the exsolved vapor phase. Magmas generated in the eastern Manus Basin inherently have high fO2 because of metasomatism of the mantle source by oxidized materials from the subducted slab, leading to copper enrichment in the magma chamber. Moreover, the presence of Cu in gas-rich melt inclusi on bubbles in Pual Ridge andesite is evidence that degassing and partitioning of Cu into the magmatic volatile phase has occurred in the eastern Manus Basin. Numerical mass balance modeling indicates that approximately 0.236 Mt Cu was potentially transferred to the hydrothermal system per cubic kilometer magma. Magmatic degassing seems to play a more significant role than leaching.

Towards wearable and implantable continuous drug monitoring:A review

Continuous drug monitoring is a promising alternative to current therapeutic drug monitoring strategies and has a strong potential to reshape our understanding of pharmacokinetic variability and to improve individualised therapy.This review highlights recent advances in biosensing technologies that support continuous drug monitoring in real time.We focus primarily on aptamer-based biosensors,wearable and implantable devices.Emphasis is given to the approaches employed in constructing biosensors.We pay attention to sensors’biocompatibility,calibration performance,long-term characteristics stability and measurement quality.Last,we discuss the current challenges and issues to be addressed in continuous drug monitoring to make it a promising,future tool for individualised therapy.The ongoing efforts are expected to result in fully integrated implantable drug biosensing technology.Thus,we may anticipate an era of advanced healthcare in which wearable and implantable biochips will automatically adjust drug dosing in response to patient health conditions,thus enabling the management of diseases and enhancing individualised therapy.

4.096 Tbit/s multidimensional multiplexing signals transmission over 1000 km few mode fiber

We experimentally transmit eight wavelength-division-multiplexing(WDM)channels,16 quadratic-amplitude-modulation(QAM)signals at 32-GBaud,over 1000 km few mode fiber(FMF).In this experiment,we use WDM,mode division multiplexing,and polarization multiplexing for signal transmission.Through the multiple-input-multiple-output(MIMO)equalization algorithms,we achieve the total line transmission rate of 4.096 Tbit/s.The results prove that the bit error rates(BERs)for the16QAM signals after 1000 km FMF transmission are below the soft-decision forward-error-correction(SD-FEC)threshold of2.4×10^(-2),and the net rate reaches 3.413 Tbit/s.Our proposed system provides a reference for the future development of high-capacity communication.

Anti-PD-L1 antibody enhances curative effect of cryoablation via antibody-dependent cell-mediated cytotoxicity mediating PD-L1^(high)CD11b^(+)cells elimination in hepatocellular carcinoma

Cryoablation(CRA)and microwave ablation(MWA)are two main local treatments for hepatocellular carcinoma(HCC).However,which one is more curative and suitable for combining with immunotherapy is still controversial.Herein,CRA induced higher tumoral PD-L1 expression and more T cells infiltration,but less PD-L1^(high)CD11b^(+)myeloid cells infiltration than MWA in HCC.Furthermore,CRA had better curative effect than MWA for anti-PD-L1 combination therapy in mouse models.Mechanistically,anti-PD-L1 antibody facilitated infiltration of CD8^(+)T cells by enhancing the secretion of CXCL9 from cDC1 cells after CRA therapy.On the other hand,anti-PD-L1 antibody promoted the infiltration of NK cells to eliminate PD-L1^(high)CD11b^(+)myeloid cells by antibody-dependent cell-mediated cytotoxicity(ADCC)effect after CRA therapy.Both aspects relieved the immunosuppressive microenvironment after CRA therapy.Notably,the wild-type PD-L1 Avelumab(Bavencio),compared to the mutant PD-L1 atezolizumab(Tecentriq),was better at inducing the ADCC effect to target PD-L1^(high)CD11b^(+)myeloid cells.Collectively,our study uncovered the novel insights that CRA showed superior curative effect than MWA in combining with anti-PD-L1 antibody by strengthening CTL/NK cell immune responses,which provided a strong rationale for combining CRA and PD-L1 blockade in the clinical treatment for HCC.

Photonics 60 GBaud PDM-16QAM fiber-wireless 2×2 MIMO delivery at THz-band

The terahertz photonics technique has bright application prospects in future sixth-generation(6G)broadband communication.In this study,we have experimentally demonstrated a photonics-assisted record-breaking net bit rate of 417 Gbit/s per wavelength signals delivery in a fiber-wireless converged communication system supported by advanced digital-signalprocessing(DSP)algorithms and a polarization multiplexing-based multiple-input multiple-output(MIMO)scheme.In the experiment,up to 60 GBaud(480 Gbit/s)polarization-division-multiplexing 16-ary quadrature-amplitude-modulation(PDM16QAM)signals are transmitted over 20 km fibers and 3 m wireless 2×2 MIMO links at 318 GHz with the bit error rate(BER)under 1.56×10^(−2).It is the first demonstration to our knowledge of signals delivery exceeding 400 Gbit/s per wavelength in a photonics-assisted fiber-wireless converged 2×2 MIMO communication system.

Thermal reffusivity： uncovering phonon behavior, structural defects, and domain size

To understand the relation between different nanostructures and thermal properties, a simple yet effective model is in demand for characterizing the underlying phonons and electrons scattering mechanisms. Herein, we make a systematic review on the newly developed thermal reffusivity theory. Like electrical resistivity which has been historically used as a theory for analyzing structural domain size and defect levels of metals, the thermal reffusivity can also uncover phonon behavior, structure defects and domain size of materials. We highlight that this new theory can be used for not only metals, but also nonmetals, even for amorphous materials. From the thermal reffusivity against temperature curves, the Debye temperature of the material and the ideal thermal diffusivity of single perfect crystal can be evaluated. From the residual thermal reffusivity at the 0 K limit, the structural thermal domain （STD） size of crystalline and amorphous materials can be obtained. The difference of white hair and normal black hair from heat conduction perspective is reported for the first time. Loss of melanin results in a worse thermal protection and a larger STD size in the white hair. By reviewing the different variation of thermal reffusivity against decreasing temperature profiles, we conclude that they reflected the structural connection in the materials. Ultimately, the future application of thermal reffusivity theory in studying 2D materials and amorphous materials is discussed.

Delivery of 40 Gbit/s W-band signal over 4600 m wireless distance employing advanced digital signal processing

We experimentally built a photonics-aided long-distance large-capacity millimeter-wave wireless transmission system and demonstrated a delivery of 40 Gbit/s W-band 16-ary quadrature amplitude modulation(QAM)signal over 4600 m wireless distance at 88.5 GHz.Advanced offline digital signal processing algorithms are proposed and employed for signal recovery,which makes the bit-error ratio under 2.4×10^(−2).To the best of our knowledge,this is the first field-trial demonstration of>4 km W-band 16QAM signal transmission,and the result achieves a record-breaking product of wireless transmission capacity and distance,i.e.,184(Gbit/s)·km,for high-speed and long-distance W-band wireless communication.

Production of jet fuel intermediates from biomass platform compounds via aldol condensation reaction over iron-modified MCM-41 lewis acid zeolite

Liquid fuel intermediates could be produced via aldol condensation reaction between furfural or 5-hydroxymethylfurfural(HMF)and acetone.It was found that iron-modified MCM-41 zeolite can be an effective Lewis acid catalyst for C-C bond formation via aldol condensation of furfural or HMF with acetone.The 4-(2-furyl)-3-buten-2-one and 1,5-di-2-furanyl-1,4-pentadien-3-one(FAc and F_(2)Ac),or 1,5-di-2-furanyl-1,4-pentadien-3-one and 1,5-bis[(5-hydroxlmethyl)-2-furanyl]-1,4-pentadien-3-one(HAc and H_(2)Ac),as two main condensation products of furfural with acetone or HMF with acetone,were observed.After 24 h at 160℃,86.9%conversion of furfural with 60.0%yield of the FAc as well as 7.5%yield of the F_(2)Ac and 88.9%conversion of the HMF with 41.1%yield of the HAc as well as 3.5%yield of the H_(2)Ac were achieved.Although furfural or HMF conversion was almost same after 24 h at 160℃,iron-modified MCM-41 zeolite catalyst displayed an enhanced selectivity to condensation products of furfural with acetone.In addition,catalysts showed an improved selectivity to the F_(2)Ac and H_(2)Ac at higher reaction temperature.The reusability and regeneration studies showed that iron-modified MCM-41 zeolite catalyst could not be reused directly,but could be regenerated by calcination in air,and the catalytic perfor-mance of regenerated catalyst was acceptable.

深圳西丽文体中心

深圳是中国发展最快的城市之一，其社会经济模式正在由传统生产型向知识研发型转变。毗邻大沙河绿色走廊的一个住宅密集区内，北望羊台山，南眺大南山公园，一个新型的文化体育中心即将落成。本案将成为一个集体育，健康，娱乐，文化于一体的多元化体验中心，试图在自然，体育，文化之间建立起深层联系。