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81.
Mn4+-activated double perovskite phosphors with composition diversity have presented excellent luminescent performances. However, the charge imbalance between Mn4+ and matrix cations would increase non-radiative recombination and reduce the structural stability. Here, novel high-efficiency stable Li+/Mn4+ co-incorporated Sr2YSbO6 red phosphors are successfully synthesized via a solid-state reaction method for warm w-LEDs, where the Li+ ions have the effect of charge balance for Sr2YSbO6:Mn4+ and reduce the non-radiative energy transfer among Mn4+ ions. It is demonstrated that the substitution of Li+–Mn4+ pairs for Sb5+ can enhance the bonding with low-shifted diffraction peaks and high emission intensity, and prolong the decay lifetime, compared with those of Mn4+ single-doped ones. Impressively, the thermal stability is enhanced to 89.72% from 84.61% at the original value of 303 K. Finally, a w-LED device based on the optimal phosphor Sr2YSbO6:0.01Mn4+/0.01Li+ red component exhibits a correlated color temperature of 4487 K and color rendering index of 80.2. Therefore, the incorporated Li+ ions serve as both charge compensator and co-activator in Mn4+-activated double perovskite phosphors with the aim of high luminescent performance and thermal stability. 相似文献
82.
83.
Jiraya Kiriratnikom Xun Zhang Xiaohan Cao Bo Chu Chengjian Zhang Xinghong Zhang 《Journal of polymer science. Part A, Polymer chemistry》2022,60(15):2262-2268
Facile construction of sulfur-rich polymers using readily available raw chemicals is an area aggressively pursued but challenging. Herein we use common feedstocks of ethylene oxide (EO), propylene oxide (PO), and carbonyl sulfide (COS) to synthesize copoly(thioether)s which are traditionally produced from unpleasant and difficult to store episulfides. In this protocol, the EO/COS coupling selectively generates a pure poly(ethylene sulfide) (PES) with melting temperature (Tm) values up to 172°C and high yields up to 98%. The EO/PO/COS terpolymerization leads to the incorporation of soft poly(propylene sulfide) (PPS) and hard PES segments together, affording a random PES-co-PPS copoly(thioether) with the complete consumption of EO and PO. Additionally, by simply varying the EO/PO feeding ratio, the obtained copoly(thioether)s possess tunable thermal properties, Tm values in the range of 76–144°C, and excellent solubility. These copolymerizations are conducted in one-pot/one-step at industrially favored reaction temperatures of 100–120°C using catalysts of common organic bases, suggesting a facile and practical manner. Especially, the copoly(thioether) exhibits high refractive indices up to 1.68 owing to its high sulfur content, suggesting a broad application prospect in optical materials. 相似文献
84.
Daniel T. W. Chu 《Journal of heterocyclic chemistry》1985,22(4):1033-1034
An efficient and regiospecific synthesis of 1-methylamino-6-fluoro-7-(4-methylpiperizin-1-yl)-1,4-dihydro-4-oxoquinoline-3-carboxylic acid ( 3 ) via an intramolecular nucleophilic displacement cyclization reaction is reported. 相似文献
85.
86.
Fossil fuels are expected to be the major source of energy for the next few decades. However, combustion of nonrenewable resources leads to the release of large quantities of CO2, the primary greenhouse gas. Notably, the concentration of CO2 in the atmosphere is increasing annually at an astounding rate. Electrochemical CO2 reduction (ECR) to value-added fuels and chemicals using electricity from intermittent renewable energy sources is a carbon-neutral method to alleviate anthropogenic CO2 emissions. Despite the steady progress in the selective generation of C1 products (CO and formic acid), the production of multi-carbon species still suffers from low selectivity and efficiency. As an ECR product, ethylene (C2H4) has a higher energy density than do C1 species and is an important industrial feedstock in high demand. However, the conversion of CO2 to C2H4 is plagued by low productivity and large overpotential, in addition to the severe competing hydrogen evolution reaction (HER) during the ECR. To address these issues, the design and development of advanced electrocatalysts are critical. Here, we demonstrate fine-tuning of ECR to C2H4 by taking advantage of the prominent interaction of Cu with shape-controlled CeO2 nanocrystals, that is, cubes, rods, and octahedra predominantly covered with (100), (110), and (111) surfaces, respectively. We found that the selectivity and activity of the ECR depended strongly on the exposed crystal facets of CeO2. The overall ECR Faradaic efficiency (FE) over Cu/CeO2(110) (FE ≈ 56.7%) surpassed that of both Cu/CeO2(100) (FE ≈ 51.5%) and Cu/CeO2(111) (FE ≈ 48.4%) in 0.1 mol·L-1 KHCO3 solutions with an H-type cell. This was in stark contrast to the exclusive occurrence of the HER over pure carbon paper, CeO2(100), CeO2(110), and CeO2(111). In particular, the FE toward C2H4 formation and the partial current density increased in the sequence Cu/CeO2(111) < Cu/CeO2(100) < Cu/CeO2(110) within applied bias potentials from -1.00 to -1.15 V (vs. the reversible hydrogen electrode), reaching 39.1% over Cu/CeO2(110) at a mild overpotential (1.13 V). The corresponding values for Cu/CeO2(100) and Cu/CeO2(111) were FEC2H4 ≈ 31.8% and FEC2H4 ≈ 29.6%, respectively. The C2H4 selectivity was comparable to that of many reported Cu-based electrocatalysts at similar overpotentials. Furthermore, the FE for C2H4 remained stable even after 6 h of continuous electrolysis. The superior ECR activity of Cu/CeO2(110) to yield C2H4 was attributed to the metastable (110) surface, which not only promoted the effective adsorption of CO2 but also remarkably stabilized Cu+, thereby boosting the ECR to produce C2H4. This work offers an alternative strategy to enhance the ECR efficiency by crystal facet engineering. 相似文献
87.
Yu Fu Yanyan Yang Dongxue Chu Zefeng Liu Lili Zhou Xiaoyang Yu Xiaoshu Qu 《Molecules (Basel, Switzerland)》2022,27(13)
Polyoxometalates (POMs) demonstrate potential for application in the development of integrated smart energy devices based on bifunctional electrochromic (EC) optical modulation and electrochemical energy storage. Herein, a nanocomposite thin film composed of a vanadium-substituted Dawson-type POM, i.e., K7[P2W17VO62]·18H2O, and TiO2 nanowires were constructed via the combination of hydrothermal and layer-by-layer self-assembly methods. Through scanning electron microscopy and energy-dispersive spectroscopy characterisations, it was found that the TiO2 nanowire substrate acts as a skeleton to adsorb POM nanoparticles, thereby avoiding the aggregation or stacking of POM particles. The unique three-dimensional core−shell structures of these nanocomposites with high specific surface areas increases the number of active sites during the reaction process and shortens the ion diffusion pathway, thereby improving the electrochemical activities and electrical conductivities. Compared with pure POM thin films, the composite films showed improved EC properties with a significant optical contrast (38.32% at 580 nm), a short response time (1.65 and 1.64 s for colouring and bleaching, respectively), an excellent colouration efficiency (116.5 cm2 C−1), and satisfactory energy-storage properties (volumetric capacitance = 297.1 F cm−3 at 0.2 mA cm−2). Finally, a solid-state electrochromic energy-storage (EES) device was fabricated using the composite film as the cathode. After charging, the constructed device was able to light up a single light-emitting diode for 20 s. These results highlight the promising features of POM-based EES devices and demonstrate their potential for use in a wide range of applications, such as smart windows, military camouflage, sensors, and intelligent systems. 相似文献
88.
Kuanda Xu Shisheng Zheng Yang Li Honghao Chu Qi Xiong Zongwei Mei Qinghe Zhao Luyi Yang Shunning Li Feng Pan 《中国化学快报》2022,33(1):424-427
The electroreduction of CO2(CO2RR) into value-added chemicals is a sustainable strategy for mitigating global warming and managing the global carbon balance. However, developing an efficient and selective catalyst is still the central challenge. Here, we developed a simple two-step pyrolysis method to confine low-valent Ni-based nanoparticles within nitrogen-doped carbon(Ni-NC). As a result, such Ni-based nanoparticles can effectively reduce CO2 to CO, with a max... 相似文献
89.
CO2的有效利用有助于解决环境和生态问题.碳酸酐酶(CA)等酶分子可精准活化CO2分子以降低反应能垒,为CO2的高效和高选择性转化提供了一种有前景的途径.然而,酶离开生物体后易失活,且难以重复利用.目前,包埋型固定化酶是常用且有效的提高酶稳定性与回用率的方法之一,但载体的存在会造成反应物CO2内扩散阻力增加,降低反应活性.此外,CO2酶促转化是一个气-液-固三相反应过程,反应体系中CO2的外扩散性能也需要加强.金属有机骨架(MOFs),特别是咪唑酯骨架(ZIFs),常被用作酶固定化的载体.ZIFs的拓扑结构可被设计成不同形貌,进而通过ZIFs的结构工程来加强分子向其中的内扩散.Pickering乳液是指以固体颗粒代替常规表面活性剂而稳定的乳液.当固体颗粒具有催化活性时,催化剂颗粒会扩大液-液-固或气-液-固三相接触面积,从而有效协调反应物在不同相中的扩散时间.如果酶被用作这些颗粒的活性中心,所制备的Pickering乳液也可能具备类似的特性,可加强底物分子向酶的外扩散.本文选择两种具有不同结构的ZIFs(ZIF-L和ZIF-8),原位包埋CA后形成CA@ZIFs颗粒以稳定Pickeirng乳液.ZIF-L和CA@ZIF-L颗粒显示出独特的二维层状堆叠结构.ZIF-8和CA@ZIF-8颗粒呈棱角清晰的十二面体结构.与CA@ZIF-8颗粒相比,CA@ZIF-L颗粒显示出更大的孔径和更宽的孔径分布,这有助于CO2从CA@ZIF-L颗粒表面扩散至酶活性中心.利用酶活测试来研究内扩散是否通过结构工程得到了加强,发现CA@ZIF-L颗粒的活性比CA@ZIF-8颗粒高22.3%,推测这是由于CA@ZIF-L颗粒特殊的十字花状结构会缩短CO2从颗粒表面扩散至酶活性中心的距离.同时,十字花状结构可暴露更多的酶活性位点(CA@ZIF-L颗粒的暴露面积是CA@ZIF-8颗粒的~8倍),从而提升了反应物浓度并显示出更高的催化活性.本文还设计了吸附实验来进一步验证上述假设,发现BSA@ZIF-L颗粒对香豆素的吸附率远高于BSA@ZIF-8颗粒,说明与ZIF-8相比,酶包埋于ZIF-L具有更强的捕获小分子的能力,表明CO2分子向CA@ZIF-L的扩散速度更快,即CA@ZIF-L的十字花状结构可强化系统的内扩散过程.进一步比较了PIBS和游离多酶体系的催化活性,将CO2通入每个系统,在反应前20 min,PIBS的pH值下降速度比游离体系快得多,说明PIBS通过在气相和液相间构建更大的界面,缩短了CO2向CA的扩散距离,从而提高了催化效率,促进了CO2转化.上述假设也通过扩散动力学的计算得到了验证.为进一步研究PIBS的CO2矿化能力,本文开展了CaCO3矿化反应,发现PIBS的CaCO3产量远高于游离多酶体系,表明构建的PIBS在强化内外扩散方面具有显著优势.最后,评估了PIBS在工业应用中的性能,由CA@ZIF-L和CA@ZIF-8颗粒构建的PIBS显示出较好的可回收性,在第8个循环后,PIBS仍可保持8.9 mg/5 min的CaCO3产量.综上,PIBS可为CO2的酶促转化和框架提供一个新方法和新平台. 相似文献
90.
Saiji Shen Chu Wu Yinghui Shang Hongdou Shen Yue Liao Yuting Guo Min Hu Xia Wang Gang Li Qigang Wang 《中国科学:化学(英文版)》2022,65(1):153-161
There are several natural materials which have evolved functional gradients,ingeniously attaining maximal efficacy from limited components.Herein,we utilized the spatiotemporal distribution of initiator acetylacetone to regulate the multienzyme polymerization and fabricate a chitosan-polymer hydrogel.The temporal priority order of acetylacetone was higher than phenolmodified chitosan by density functional theory calculation.The acetylacetone within the gelatin could gradually diffuse spatially into the chitosan hydrogel to fabricate the composite hydrogel with gradient network structure.The gradient hydrogel possessed a transferring topography from the two-dimensional pattern.A continuously decreased modulus along with acetylacetone diffusion was confirmed by atomic force microscope-based force mapping experiment.The water-retaining ability of various regions was confirmed by low-field nuclear magnetic resonance(NMR)and thermogravimetric analysis(TG)analysis,which led to the spontaneous actuation of gradient hydrogel with maximum 1821°/h curling speed and 227°curling angle.Consequently,the promising gradient hydrogels could be applied as intelligent actuators and flexible robots. 相似文献