共价有机框架负载贵金属铂用于电催化析氢

本工作探究了共价有机框架负载贵金属Pt的电催化析氢性能。以2, 6-二氨基蒽醌和2,4,6-三甲酰基间苯三酚为构筑单元,采用溶剂热法合成了TP-DAAQ COF。随后通过金属前驱体浸渍法制备了Pt-TP-DAAQ COF。X射线粉末衍射,傅里叶红外光谱,氮气吸附/脱附等表明成功制备了TP-DAAQ COF和Pt-TP-DAAQ COF。电化学测试结果表明Pt-TP-DAAQ COF (其中含有5.8%的Pt)展现了比20% Pt/C还优异的电催化活性。当电流密度为10 mA cm?2时,Pt-TP-DAAQ COF的过电位为45 mV,Tafel 斜率为29 mV dec?1。这高效的电催化活性源于TP-DAAQ COF与Pt之间良好的协同效应。Pt-TP-DAAQ COF具有较大的比表面积和规整的一维孔道,使催化位点更易于与电解液中的物质发生接触和相互作用,从而增强了其催化性能。     

基于醌基的共价有机框架用于电催化析氧反应

将蒽醌作为构筑单元设计合成了醌基功能化的新型2,6-二氨基蒽醌共价有机框架(DAAQ-COF). 粉末X射线衍射、 氮气吸附-脱附、 红外和热重等分析结果表明, DAAQ-COF具有高的结晶度和比表面积(577 m²/g). 此外, 醌基功能化的无金属DAAQ-COF显示出高的析氧反应(OER)活性(10 mA/cm²下, 过电位389 mV, Tafel斜率135 mV/dec). 这源于引入的醌基基团有效改变了COF框架的电子结构和化学特性, 加上COF材料本身的高结晶度和比表面积, 使得反应物能更有效地与活性位点接触, 从而促进OER进程. 这些结果表明合理地设计功能化的COF材料能够进一步推动此类材料在电催化领域的应用.     

共价有机框架材料在光催化领域中的应用

共价有机框架(COFs)材料是有机构筑基元通过共价键连接而形成的晶态有机多孔材料. COFs具有孔道结构规整、及比表面积高等特点,被广泛地应用于气体储存与分离、催化、传感、储能及光电转化等领域.将具有可调吸光能力的有机构筑基元引入到COFs中,可使其展现出强大的光催化潜力.近年来, COFs在光催化领域中发展迅猛.本文总结了COFs在光催化产氢、光催化二氧化碳还原、光催化有机反应以及光催化污染物降解等方面的研究进展,并展望了其在光催化领域的应用前景.     

二维共价有机框架材料的可控合成及其光催化应用研究进展

通过模拟自然界光合作用, 将太阳能转化为方便存储的化学能是缓解未来能源短缺和环境污染问题的理想途径之一. 二维共价有机框架材料(2D COFs)是近年来发展起来的一类新型有机半导体材料, 具有结晶度高、结构精确以及化学组分灵活可调等优势, 在光催化领域展现出巨大应用潜力, 受到了研究者们的广泛关注. 对2D COFs的可控制备以及电子结构调控方法进行了系统总结, 并重点介绍了它们在光催化水分解、CO₂还原以及H₂O₂合成领域的最近研究进展, 讨论了材料结构和催化性能之间的关系, 最后对2D COFs在光催化应用领域存在的机遇和挑战进行了展望.     

基于四硫富瓦烯的无金属共价有机框架材料用于高效电催化析氧反应

共价有机框架(COFs)在电催化析氧反应(OER)中的应用得到了广泛的关注。然而,大多数无金属共价有机框架(COFs)的导电性较差,不利于OER反应。四硫富瓦烯(TTF)是一种良好的电子供体,具有快速的电子转移能力,将TTF整合到共价有机框架骨架中将有助于电子的转移。在此,我们报道了一种基于四硫富瓦烯的二维无金属共价有机框架材料,JUC-630。与不含四硫富瓦烯的同类材料(Etta-Td COF)相比,JUC-630具有较低的过电位(400 mV)和塔菲尔斜率(104 mV∙dec⁻¹)。本研究提出了合理设计功能基元的策略,这有助于大大提高COF材料的OER催化活性。     

具有可控载流子动力学的烯烃连接的共价有机框架用于高效太阳能光催化制氢（英文）

太阳能光催化水直接制氢被认为是未来解决全球能源危机和环境污染问题的有效途径之一.COFs是一类新兴的有机结晶多孔聚合物光催化剂,具有巨大的发展空间.当前研究最多的是亚胺键连接的COFs光催化剂,其骨架的π-共轭程度相对较低,且亚胺键上的氮容易受到质子攻击,会影响光化学过程和光催化性能.烯烃(C=C键)连接的COFs是全π-共轭的,具有促进的载流子迁移率和超高的化学稳定性,是极具潜力的光催化反应平台.然而,由于C=C键的不可逆特性,成功构筑具有高结晶度和孔隙率的烯烃连接的COFs仍极具挑战.构建D-A结构被认为是提升其光催化活性的有效策略之一,但目前具有D-A结构的烯烃连接的COFs光催化研究较少.本文提出了一种简单的分子工程策略来调控烯烃连接COFs的D-A相互作用以实现高效的光催化产氢.将2,4,6-三甲基1,3,5-三嗪(TM)分别与对苯二甲醛(TA)、 2,5-二甲基对苯二甲醛(MA)和3,3’-二甲基-4,4’-二醛基联苯(DMA)通过Knoevenagel聚合反应制备三种D-A型烯烃连接的COFs,即TM-TA-COF, TM-MA-COF和TM-DMA-COF,系统考察了引...     

卟啉-硫醚基共价有机框架材料用于氧还原反应电催化剂

氧还原反应（ORR）是能进行能量存储的核心电化学过程。由于它的动力学速率缓慢,因此亟需制备出高活性的电催化剂来促进这一反应的速率。二维共价有机框架材料（2D COFs）的π-π堆积结构可赋予骨架高导电率,并且一维有序的孔道有利于促进中间反应体传输。因此,其在可再生能源领域中具有良好的应用前景,并有望作为能量存储与转化的强大催化平台。本文通过向2D COFs中引入金属卟啉单元及硫醚单元成功制备了两个2D COFs （JUC-600和JUC-601）。通过多种表征手段证明,这两个2D COFs均具有AA堆积的sql拓扑结构。通过电化学测试表明,Co²⁺配位的JUC-601具有更正的ORR起始电势（0.825 V）和半波电势（0.7 V）、更高的活性表面积（7.8 mF/cm²）,更低的Tafel斜率（58 mV/dec）。这主要是由于JUC-601的高比表面积和高孔隙率使得中间产物能更易在COFs的表面和孔道中接触和传输。此外,Co²⁺-卟啉单元以及硫醚单元的存在使其骨架整体的电子结构发生了变化,更有利于电子转移。这一工作不仅开发了新的二维卟啉-硫醚基COFs材料,同时也拓展了2D COFs材料在电催化领域的应用。     

Precise Design of Covalent Organic Frameworks for Electrocatalytic Hydrogen Peroxide Production

Electrochemical synthesis of H₂O₂ with high productivity is a significant challenge in electrocatalysis. Herein, we develop Mg-ion contained covalent organic frameworks (MgP-DHTA-COF), comprising stacked 2D layers, well-defined skeletons, and well-ordered monodispersed active sites, for the electrocatalytic production of H₂O₂ directly from O₂ and H₂O. The precise-designed MgP-DHTA-COF achieves H₂O₂ selectivity up to 96%, high Faradaic efficiency of 91% and reliable stability for H₂O₂ synthesis in 0.10 mol L⁻¹ KOH aqueous solution. Both experiments and simulations demonstrate that the pyrrolic-N fixed Mg ions in the knots promote the reactivity of COF and enhance the adsorption ability of OOH*. This work provides a valuable example for the design of an efficient electrocatalyst based on COFs for H₂O₂ production.     

Donor-Acceptor Type Covalent Organic Frameworks

Intermolecular charge transfer (ICT) effect has been widely studied in both small molecules and linear polymers. Covalently-bonded donor-acceptor pairs with tunable bandgaps and photoelectric properties endow these materials with potential applications in optoelectronics, fluorescent bioimaging, and sensors, etc. However, owing to the lack of charge transfer pathway or effective separation of charge carriers, unfavorable charge recombination gives rise to inevitable energy loss. Covalent organic frameworks (COFs) can be mediated with various geometry- and property-tailored building blocks, where donor (D) and acceptor (A) segments are connected by covalent bonds and can be finely arranged to form highly ordered networks (namely D−A COFs). The unique structural features of D−A COFs render the formation of segregated D−A stacks, thus provides pathways and channels for effective charge carriers transport. This review highlights the significant progress on D−A COFs over the past decade with emphasis on design principles, growing structural diversities, and promising application potentials.     

Vinylene-Linked Covalent Organic Frameworks (COFs) with Symmetry-Tuned Polarity and Photocatalytic Activity

The polarity of a semiconducting molecule affects its intrinsic photophysical properties, which can be tuned by varying the molecular geometry. Herein, we developed a D_3h-symmetric tricyanomesitylene as a new monomer which could be reticulated into a vinylene-linked covalent organic framework (g-C₅₄N₆-COF) via Knoevenagel condensation with another D_3h-symmetric monomer 2,4,6-tris(4′-formyl-biphenyl-4-yl)-1,3,5-triazine. Replacing tricyanomesitylene with a C_2v-symmetric 3,5-dicyano-2,4,6-trimethylpyridine gave a less-symmetric vinylene-linked COF (g-C₅₂N₆-COF). The octupolar conjugated characters of g-C₅₄N₆-COF were reflected in its scarce solvatochromic effects either in ground or excited states, and endowed it with more promising semiconducting behavior as compared with g-C₅₂N₆-COF, such as enhanced light-harvesting and excellent photo-induced charge generation and separation. Along with the matched energy level, g-C₅₄N₆-COF enabled the two-half reactions of photocatalytic water splitting with an average O₂ evolution rate of 51.0 μmol h⁻¹ g⁻¹ and H₂ evolution rate of 2518.9 μmol h⁻¹ g⁻¹. Such values are among the highest of state-of-the-art COF photocatalysts.     

Covalent Organic Frameworks toward Diverse Photocatalytic Aerobic Oxidations

Photoactive two-dimensional covalent organic frameworks (2D-COFs) have become promising heterogenous photocatalysts in visible-light-driven organic transformations. Herein, a visible-light-driven selective aerobic oxidation of various small organic molecules by using 2D-COFs as the photocatalyst was developed. In this protocol, due to the remarkable photocatalytic capability of hydrazone-based 2D-COF-1 on molecular oxygen activation, a wide range of amides, quinolones, heterocyclic compounds, and sulfoxides were obtained with high efficiency and excellent functional group tolerance under very mild reaction conditions. Furthermore, benefiting from the inherent advantage of heterogenous photocatalysis, prominent sustainability and easy photocatalyst recyclability, a drug molecule (modafinil) and an oxidized mustard gas simulant (2-chloroethyl ethyl sulfoxide) were selectively and easily obtained in scale-up reactions. Mechanistic investigations were conducted using radical quenching experiments and in situ ESR spectroscopy, all corroborating the proposed role of 2D-COF-1 in photocatalytic cycle.     

Graphene Oxide-Assisted Covalent Triazine Framework for Boosting Photocatalytic H2 Evolution

Covalent triazine frameworks (CTFs) with two-dimensional structures have exhibited promising visible-light-induced H₂ evolution performance. However, it is still a challenge to improve their activity. Herein, we report π-conjugation-linked CTF-1/GO for boosting photocatalytic H₂ evolution. The CTF-1/GO hybrid material was obtained by a facile low-temperature condensation of 1,4-dicyanobenzene in the presence of GO. The results of photocatalytic H₂ evolution indicate that the optimum hybrid, CTF-1/GO-3.0, exhibited an H₂ evolution rate of 2262.4 μmol ⋅ g⁻¹ ⋅ h⁻¹ under visible light irradiation, which was 9 times that of pure CTF-1. The enhanced photocatalytic performance could be attributed to the fact that GO in CTF-1/GO hybrids not only acts as an electron collector and transporter like a “bridge” to facilitate the separation and transfer of photogenerated charges but also shortens the electron migration path due to its thin sheet layer uniformly distribution over CTF-1. This work could help future development of novel conjugated CTF-based composite materials as high-efficiency photocatalyst for photocatalysis.     

Crystalline Covalent Triazine Frameworks by In Situ Oxidation of Alcohols to Aldehyde Monomers

Covalent triazine frameworks (CTFs) with aromatic triazine linkages have recently received increasing interest for various applications because of their rich nitrogen content and high chemical stability. Owing to the strong aromatic C=N bond and high chemical stability, only a few CTFs are crystalline, and most CTFs are amorphous. Herein we report a new general strategy to give highly crystalline CTFs by in situ formation of aldehyde monomers through the controlled oxidation of alcohols. This general strategy allows a series of crystalline CTFs with different monomers to be prepared, which are shown to have higher thermal stability and enhanced performance in photocatalysis as compared with the less crystalline or amorphous CTFs. This open‐system approach is very simple and convenient, which presents a potential pathway to large‐scale industrial production of crystalline CTFs.     

Regenerable Covalent Organic Frameworks for Photo-enhanced Uranium Adsorption from Seawater

Uranium is a key resource for the development of the nuclear industry, and extracting uranium from the natural seawater is one of the most promising ways to address the shortage of uranium resources. Herein, a semiconducting covalent organic framework (named NDA-TN-AO) with excellent photocatalytic and photoelectric activities was synthesized. The excellent photocatalytic effect endowed NDA-TN-AO with a high anti-biofouling activity by generating biotoxic reactive oxygen species and promoting photoelectrons to reduce the adsorbed U^VI to insoluble U^IV, thereby increasing the uranium extraction capacity. Owing to the photoinduced effect, the adsorption capacity of NDA-TN-AO to uranium in seawater reaches 6.07 mg g⁻¹, which is 1.33 times of that in dark. The NDA-TN-AO with enhanced adsorption capacity is a promising material for extracting uranium from the natural seawater.