Zr-MOF空心纳米球固载离子液体对CO2环加成反应的催化性能

通过后合成修饰方法(PSM)构筑了空心纳米球(Void@UiO-66-Ⅰ)和实心块(UiO-66-Ⅰ) 2种形貌的季铵盐功能化UiO-66-NH₂(Zr), 得到兼具酸碱活性位点和氢键给体的新型功能化金属-有机框架材料. 通过一系列表征证明2种催化剂的成功合成, 并将它们用于催化转化CO₂和氧化苯乙烯的环加成反应. 由于Void@UiO-66-Ⅰ催化剂的季铵盐部分含有大量的羟基和卤素阴离子, 可以通过氢键和亲核攻击与环氧化合物连接, 诱导环氧化合物开环, 促使反应顺利进行, 且催化剂的中空结构有利于物质进出催化剂, 起到加快反应速率的作用, 使得该催化剂在CO₂与氧化苯乙烯环加成反应中表现出比实心块UiO-66-Ⅰ催化剂更好的催化性能. Void@UiO-66-Ⅰ催化剂在120 ℃, CO₂压力为1.2 MPa, 反应时间为6 h, 无溶剂和助催化剂的反应条件下, 碳酸苯乙烯酯的收率和选择性分别为85.5%和95%.     

柔性电子学中的表界面化学

柔性电子作为新兴的研究热点, 涉及材料、 化学、 物理等多个基础学科的交叉, 以及在生物医用、 可穿戴设备及人工智能等多个领域的应用. 柔性电子设备的制造加工过程中会用到弹性基底、 导电层、 功能层等多种性质各异的材料, 其互相之间的整合受到它们表面性质和界面结合力的限制; 器件的功能、 可靠性、 对环境的敏感性等也受到了器件表界面性质的影响; 因此, 对材料和器件表界面的处理在柔性电子学中具有重要作用. 本文对柔性电子学中常用的表界面化学过程分为3大类进行介绍: 表面电化学过程, 基于特定化合物反应产生的电流制备电化学传感器, 利用电流/电压控制表面负载化合物; 表面修饰, 通过表面改性提高材料的加工性能, 共价修饰分子层或其它材料赋予器件特殊功能性质或保护层; 不同材料之间的界面连接, 通过共价连接或化学反应辅助的物理交联实现不同材料的结合, 提高柔性器件的稳定性, 实现柔性设备的整合. 对各应用进行总结和举例后, 讨论了存在的问题, 并对未来的发展方向及前景进行了展望.     

修饰吡啶衍生物的染料敏化光阳极水氧化性能的研究

染料敏化光电化学电池(DSPECs)是构建人工光合作用体系的潜在方式,其优势在于可通过优化染料结构来拓展可见光吸收范围,从根本上提高太阳能利用效率.染料敏化光阳极在受激发产生电荷分离之后,激发电子注入TiO₂半导体导带,由于其导带位置比传统的可见光半导体,如BiVO4和Fe3O4等相比较负,因此理论上可以在较小的偏压下取得较大的光电转换效率,也更有利于和光阴极相耦合实现无偏压分解水.电荷传输动力学研究表明,注入到TiO₂导带的电子向氧化态光敏剂和催化剂的回传是造成体系能量损失的主要原因,集中体现在光电流密度和效率的降低.目前,已经报道了多种手段来减少DSPECs光阳极表面的电子回传,包括使用带有长烷基链的锚定基团对水氧化催化剂进行修饰,在半导体表面引入电子中介体以及使用核-壳结构的基底等.其中,SnO2/TiO₂基底被广泛应用在染料敏化光阳极中,这种基底可以提高光生电子的注入效率,同时两种金属氧化物之间的异质结有效抑制了电子回传,从而提高了DSPECs的光电活性.然而,核-壳结构基底需要使用原子层沉积技术来制备,所以操作相对复杂.本文基于Ru-bda(bda=2,2'-联吡啶-6,6'-二羧酸)结构的分子水氧化催化剂和带有磷酸修饰基团的三联吡啶钌通过共吸附的方式制备染料敏化光阳极,在不使用核-壳结构基底的情况下,利用吡啶衍生物对TiO₂电极表面的修饰来减少电子回传.本文利用一系列吡啶衍生物作修饰负载在TiO₂光阳极上(TiO₂|RuP,1;RuP=Ru(4,4'-(PO3H2)2-2,2'-联吡啶)(2,2'-联吡啶)2;1=Ru(bda)(L)2,bda=2,2'-联吡啶-6,6'-二羧酸,L=(10-吡啶-4-基氧基)癸基)膦酸.在100 mW/cm2的白光照射下(λ>400 nm),TiO₂|RuP,1,P1(P1=4-羟基吡啶)光阳极在0.4 V(vs.NHE)的外加偏压下获得了1 mA/cm2的光电流密度,其光电流比未修饰吡啶的光阳极增加了42%.同时,其入射光子-电流转化效率在470 nm波长的单色光光照下达到最大,为13.6%.经过吡啶衍生物所修饰的光阳极光电性能和文献中利用核-壳结构基底所制备的类似光阳极性能相当,且光电流密度随吡啶对位取代基供电性能的增强而增大.瞬态吸收光谱和电化学阻抗谱测试表明,吡啶吸附在光阳极上能有效地抑制界面上的电子回传,延长电荷分离寿命,是光电流增加的根本原因,这也表明有机小分子修饰是提高染料敏化光阳极性能的简单、有效的策略.     

Mo的引入方式对CeO2脱硝性能的影响

固定源排放的氮氧化物(NOx)导致了严重的环境污染问题,NH3选择性催化还原(NH3-SCR)被认为是目前控制NOx排放的最有效技术,已广泛应用于电力行业的烟气排放治理.然而,我国非电行业的NOx减排仍然面临着重大挑战,因为其排放的废气温度通常低于300oC,且含有一定量的SO2,传统的钒基SCR催化剂因活性温度(300～400oC)较高而无法有效发挥作用.因此,亟待开发新型的高效低温SCR催化剂.铈基催化剂由于氧化铈(CeO2)的优异储氧能力(OSC)和良好的氧化还原能力而显示出较好的低温(80～300oC)脱硝性能,如Mn-Ce,W-Ce,Ta-Ce,Cu-Ce和Nb-Ce等.但这些铈基催化剂易被烟气中的SO2毒化而导致催化活性降低.因此,提高铈基SCR催化剂抗硫中毒能力是其产业化应用的关键.已有研究发现,通过构筑结构保护层或添加另一种金属来保护活性组分是提高SCR催化剂抗硫性能的一种可行策略.氧化钼(MoO3)通常被用做传统V2O5/TiO2催化剂的促进剂以提高其水热稳定性和表面酸性.研究表明,在V/Ti催化剂中引入钼物种不仅可以提高其SCR活性,而且提高了V/Ti催化剂的抗SO2性能,这是由于VMo/Ti表面较少的V–O–V键削弱了对SO2的氧化作用.Tang等开发了一种Fe2O3/MoO3纳米片催化剂,显示出比纯Fe2O3更好的抗SO2能力,主要是由于层状结构的MoO3能阻止NH4+在硫酸氢铵中的沉积.目前关于Mo的引入方式即催化剂的制备方法对铈基催化剂物化性能和NH3-SCR催化性能(特别是抗SO2能力)的影响的研究还比较少.本文分别采用浸渍法和沉淀法在CeO2中引入钼物种,制备了Mo-CeO2和MoCe-cp催化剂来探究制备方法对MoCe催化剂的脱硝性能及抗SO2中毒能力的影响.结果表明,引入Mo可以显著地提高CeO2的低温脱硝性能,其中Mo-CeO2催化剂在150 oC即可达到80％以上的脱硝效率,同时抗SO2中毒性能也得到了显著提高.对催化剂结构、氧化还原能力、表面酸度和反应物分子的吸附脱附性质进行了表征,并与MoCe催化剂脱硝性能和抗硫性能相关联.结果表明,Mo-CeO2和MoCe-cp催化剂的物理化学性质和脱硝性能有明显区别.首先,Mo-CeO2中的钼物种主要存在于CeO2表面,而MoCe-cp中的钼物种主要存在于CeO2体相,其为Mo-CeO2表面带来大量的Br?nsted酸位并抑制了硝酸盐的吸附,促使NH3-SCR反应按照Eley-Rideal机理进行,进而表现出优于MoCe-cp的低温活性.其次,Mo-CeO2表面更多的Mo物种抑制了SO2的吸附,从而使Mo-CeO2表现出更好的抗SO2性能.本文为具有实际应用前景的铈基NH3-SCR催化剂的设计提供了参考.     

Contemporary Approaches to α,β-Dehydroamino Acid Chemical Modifications

As one of the most common unnatural amino acids(uAAs), α, β-dehydroamino acids(α,β-dhAAs) can be found in various ribosomally synthesized and post-translationally modified peptides(RiPPs) and other naturally occurring peptides. In recent years, novel reactions for α,β-dhAA modification continue to emerge. Due to their unique electrophilicity different from 20 natural amino acids, α,β-dhAAs, especially dehydroalanine(Dha), have become powerful tools for site-selective protein modification. In this review, we mainly focus on the latest research progress of C-C and C-heteroatom(C-X, X=S, N, Se, Si, P, B) bond formation methods based on α,β-dhAAs in the past five years. Particularly, we pay much attention to the α,β-dhAA derivatization methodologies used in the late-stage modification for natural peptides and proteins. In addition, we also focus on the downstream functionalization and therapeutic biologic applications of these modifications.     

石榴石固体电解质Li3BO3界面改性研究

石榴石固体电解质由于其高的离子电导率,对锂金属稳定等优点成为了下一代高性能锂电池的重要研究方向之一。但锂金属负极界面浸润性与锂枝晶问题限制了其应用。本文通过简单的液相沉积结合高温烧结的方法,在石榴石固体电解质片表面构建了一层稳定的硼酸三锂(Li₃BO₃)修饰层。研究表明,Li₃BO₃修饰层可以有效改善石榴石固体电解质与锂金属负极界面接触,促进锂的均匀沉积/溶出,从而抑制锂枝晶生长,提高界面稳定性。Li₃BO₃修饰后石榴石电解质片与锂金属之间紧密结合,Li/石榴石界面阻抗由修饰前的1780 Ω·cm²降低至58 Ω·cm²。得益于界面接触的改善,Li₃BO₃修饰后的LLZTO电解质组装的对称电池可以在0.1 m·cm^-2的电流密度下稳定工作超过700 h。而未修饰的对称电池在0.05 mA·cm^-2的电流密度下短时间工作即出现微短路现象。     

Effect of Aluminum Alloy Surface Modification on Adhesion of the Modified Polyurethane Coating and Its Corrosion Protective Performance北大核心CSCD

The ordinary organic coatings on aluminum alloy usually encounter a problem of low adhesion to the substrate, which results in destruction and failure of the long-term protective performance of the anticorrosion systems. The surface modification of aluminum alloy is able to enhance the adhesion of organic coating on aluminum alloys, and to improve their protective performance. In this work, a combined surface modification of anodic oxidation and mussel adhesion protein/CeO2/3-aminopropyltriethoxysilane composite film (MCA) was developed on the aluminum alloy. The adhesion of modified polyurethane coated on the treated aluminum alloy and its corrosion protective performance were evaluated comprehensively by using contact angle, adhesion strength, electrochemical impedance spectroscopy (EIS), and scanning reference electrode technique (SRET). The measurements of EIS and SRET demonstrated that the MCA composite film on anodic oxidized Al possessed self-healing function and provided effective protection against early corrosion of aluminum alloy. The pull-off test showed that both anodic oxidation treatment and MCA composite film modification were able to increase the adhesion of modified polyurethane coating on aluminum alloy, and their combined action were supposed to remarkably enhance the adhesion strength up to 17.1 MPa. The reason for the improvement of adhesion was that the anodic oxidation treatment and MCA composite film modification could improve the surface roughness of aluminum alloy, and enhance the surface wettability and surface polarity, which is beneficent to enhance the bonding of the modified polyurethane coating to aluminum alloy surface. The EIS results showed that no any corrosion occurred for the modified polyurethane coating on the treated aluminum alloy during 65 d immersion in 3.5wt.% NaCl solution. The impedance value in low frequency range of the modified polyurethane coating always maintained at a high order of magnitude on the aluminum alloy treated by anodic oxidation and MCA composite film modification, showing an excellent protective performance of the coating system. The evaluation of Neutral Salt Spray (NSS) indicated that the modified polyurethane coating on the treated aluminum alloy owned superior corrosion protection performance, and the adhesion strength remained 13.1 MPa and no any corrosion was found at the scratch locations even after 1200 h of salt spray testing. It was concluded that combination of anodic oxidation and MCA composite film were capable of significantly improving the adhesion of modified polyurethane coating on aluminum alloy and providing long-term effective corrosion protection for aluminum alloy. © 2021 Authors. All rights reserved.     

Surface engineering of nanoparticles for highly efficient UV‐shielding composites

Overexposure to ultraviolet (UV) with high energy can not only hurt human skin but also accelerate the degradation of organic matter. Hence, the preparation of polymer‐based UV‐shielding nanocomposites has attracted substantial attention due to the low cost, easy processing and wide applications. Notably, the highly efficient UV‐shielding polymer nanocomposites are still hindered by the agglomeration of inorganic anti‐UV nanoparticles (Nps) in polymer matrix and the narrow absorption range of UV‐shielding agents. To overcome the aforementioned bottlenecks, surface engineering of anti‐UV Nps including organic modification and inorganic hybridization has been extensively employed to enhance the UV‐shielding efficiency of composites. Herein, to deliver the readers a comprehensive understanding of the surface engineering of anti‐UV Nps, we systematically summarize the recent advances in surface organic modification and inorganic hybridization related to anti‐UV Nps. The UV‐shielding mechanism and the factors affecting UV‐shielding efficiency of polymer nanocomposites are also discussed. Finally, perspectives on remaining challenges and future development of highly efficient UV‐shielding composites are outlined.     

Binding Characteristics Study of DNA based Aptamers for E. coli O157:H7

E. coli O157:H7 is a pathogenic bacterium producing verotoxins that could lead to serious complications such as hemolytic uremia syndrome. Fast detection of such pathogens is important. For rapid detection, aptamers are quickly gaining traction as alternative biorecognition molecules besides conventional antibodies. Several DNA aptamers have been selected for E. coli O157:H7. Nonetheless, there has not been a comparative study of the binding characteristics of these aptamers. In this work, we present a comprehensive analysis of binding characteristics including binding affinity (K_d) and binding capacity (B_max) of DNA-based aptamers for E. coli O157:H7 using qPCR. Our results show that aptamer E18R has the highest binding capacity to E. coli 157:H7 and the highest specificity over non-pathogenic E. coli strains K12 and DH5α. Our study also finds that the common biotin-tag modification at 5′ end typically changes the binding capacity significantly. For most of the selected aptamers, the binding capacity after a biotin-tag modification decreases. There exists a discrepancy in the binding capability between the selected aptamer and the aptamer used for detection. Our study also shows that a lower concentration of Mg²⁺ ions in the binding buffer leads to a decrease in the binding capacity of E17F and E18R, while it does not affect the binding capacity of S1 and EcoR1.     

水溶液法原位构建ZnO亲锂层稳定锂-石榴石电解质界面

固态电池以其高安全性和高能量密度而备受关注。石榴石型固体电解质(LLZO)由于具有较高的离子导电性和对锂金属的稳定性,在固态电池中具有应用前景,但陶瓷与锂金属较差的界面接触会导致高的界面阻抗和可能形成的枝晶穿透。我们利用LLZO表层独特的H⁺/Li⁺交换反应,提出了一种简便有效的金属盐类水溶液诱发策略,在电解质表面原位构建ZnO亲锂层,界面处LiZn合金化实现紧密连续的接触。引入改性层后,界面阻抗可显著降低至约10Ω·cm²,对称电池能够在0.1mA·cm^-2的电流密度下实现长达1000h的长循环稳定性。匹配正极LiFePO₄(LFP)或LiNi_0.5Co_0.2Mn_0.3O₂(NCM523)的准固态电池在室温下能够稳定循环100次以上。