磷酸锆镍的微波制备及其可见光光催化性能

以氧氯化锆、氯化镍和磷酸二氢钠为原料,在较低温度和常压条件下采用微波辅助法制备具有特殊形貌的磷酸锆镍NiZr(PO_4)_2·4H_2O。研究了3种不同种类的表面活性剂对磷酸锆镍的物相、尺寸及形貌的影响。结果表明,表面活性剂的引入可以降低磷酸锆镍颗粒的平均粒径。与十二烷基硫酸钠(SDS)相比,聚乙烯吡咯烷酮K30(PVP-K30)和十六烷基三甲基溴化铵(CTAB)对颗粒生长的抑制程度更大,从而产物的平均粒径更小。使用亚甲基蓝(MB)溶液模拟印染废水,对磷酸锆镍的光催化降解性能进行了探讨。结果表明,可见光下以PVP-K30为模板制备的磷酸锆镍对MB的表观脱色率为49.0%,优于CTAB和SDS条件下制备的磷酸锆镍。本文为新型磷酸锆类复盐的制备与应用研究提供了新的思路和方法。     

PO43-掺杂Bi2O2CO3/Bi0的制备及其可见光催化性能

构建氧空位以及附着金属单质Bi(Bi⁰)是增强半导体材料光吸收性能、促进半导体光生载流子分离的有效方法。通过简单的共沉淀法及氢气热还原成功制备了PO₄^3-掺杂Bi₂O₂CO₃附着Bi⁰(Bi-P-BOC)的可见光催化剂,并对其在可见光下催化降解氧氟沙星(OFX)的性能及机理进行了研究。材料表征结果表明BOC随着PO₄^3-的均匀掺杂,可见光吸收能力增强,表面缺陷增多,比表面积增大。而随着氢气热还原,BOC表面形成 Bi⁰的同时也原位构建了大量的氧空位。可见光催化性能测试表明,Bi-P-BOC可以在180 min内降解约85%的OFX,降解速率为0.013 0 min^-1,是BOC降解速率的8倍。Bi-P-BOC光催化降解机理表明其具有更好的可见光吸收能力,Bi⁰以及氧空位的存在促进了光生载流子的分离,h+是其光催化降解过程中的主要的活性氧物种(ROS),此外,¹O₂和·O₂^-也对降解有一定贡献。     

粉煤灰漂珠负载Bi2WO6复合材料的制备及光催化性能研究

以工业固体废弃物粉煤灰漂珠(fly ash cenospheres, FACs)为载体, 采用水热法制备了新颖的漂珠负载Bi₂WO₆复合材料(Bi₂WO₆/FACs), 通过X射线衍射(XRD), 扫描电子显微镜(SEM), X-射线光电子能谱(XPS), 和紫外-可见漫反射光谱(DRS)技术对其进行了表征。XRD数据显示了正交相Bi₂WO₆的特征衍射峰。DRS结果证实了引入FACs后Bi₂WO₆对可见光的吸收增强。在可见光的照射下, 以亚甲基蓝溶液的光催化降解评价了Bi₂WO₆/FACs复合材料的光催化性能。结果表明：Bi₂WO₆/FACs的光催化性能优于纯Bi₂WO₆的, 其一级反应速率常数(k)为后者的2.4倍。尤其是由于漂珠质轻中空的特性, Bi₂WO₆/FACS复合光催化剂可长时间漂浮于水面, 既能充分吸收光能, 又有利于催化剂的回收和重复利用。     

Photocatalytic Dye Methyl Orange Decomposition on Ternary Sulfide （CdIn2S4） under Visible-light

A novel and efficient photocatalyst, CdIn2S4, was simply prepared by a programmed temperature hydrothermal method. The product had a nanometer size （10-15 nm） and strong absorption in the range of 200 to 580 nm, and it exhibited visible-light photocatalytic activity to decompose dye methyl orange in aqueous system.     

Photocatalytic Hydrogen Production Activity and Mechanism of New Nickel-Based Sulfur Complexes in Aqueous Solution

The development of industry and the increase in population have caused energy shortages and environmental pollution problems. Developing clean and storable new energy is identified as a key way to solve the problems above. Hydrogen is viewed as the most potential energy carrier due to its high calorific value and pollution-free. To convert solar energy into hydrogen energy, three nickel-based catalysts, Ni(aps)(pys)₂ (aps=2-amino-2-phenylacetic salicylaldehyde) ( 1 ), Ni(ads)(pys)₂ (ads=aniline salicylaldehyde, pys=pyridine-2-thiolate) ( 2 ), Ni(acs)(pys)₂ (acs=aniline 5-chlorosalicylaldehyde) ( 3 ), were synthesized and explored as photocatalysts for hydrogen production. A three-component photocatalytic system for hydrogen production was constructed using target complex as photocatalyst, triethanolamine (TEOA) as electron sacrificial agent and fluorescein (FL) as photosensitizer. Under the optimum conditions, about 1504 μmol of H₂ can be obtained with 25 mg catalyst 2 after 3 hours of irradiation. Finally, the hydrogen-production mechanism was discussed by experimental and theoretical methods.     

Dual C(sp3)−H Bond Functionalization of N‐Heterocycles through Sequential Visible‐Light Photocatalyzed Dehydrogenation/[2+2] Cycloaddition Reactions

Herein we describe a mild method for the dual C(sp³)?H bond functionalization of saturated nitrogen‐containing heterocycles through a sequential visible‐light photocatalyzed dehydrogenation/[2+2] cycloaddition procedure. As a complementary approach to the well‐established use of iminium ion and α‐amino radical intermediates, the elusive cyclic enamine intermediates were effectively generated by photoredox catalysis under mild conditions and efficiently captured by acetylene esters to form a wide array of bicyclic amino acid derivatives, thus enabling the simultaneous functionalization of two vicinal C(sp³)?H bonds.     

Synthesis of β‐Substituted γ‐Aminobutyric Acid Derivatives through Enantioselective Photoredox Catalysis

β‐Substituted chiral γ‐aminobutyric acids feature important biological activities and are valuable intermediates for the synthesis of pharmaceuticals. Herein, an efficient catalytic enantioselective approach for the synthesis of β‐substituted γ‐aminobutyric acid derivatives through visible‐light‐induced photocatalyst‐free asymmetric radical conjugate additions is reported. Various β‐substituted γ‐aminobutyric acid analogues, including previously inaccessible derivatives containing fluorinated quaternary stereocenters, were obtained in good yields (42–89 %) and with excellent enantioselectivity (90–97 % ee). Synthetically valuable applications were demonstrated by providing straightforward synthetic access to the pharmaceuticals or related bioactive compounds (S)‐pregabalin, (R)‐baclofen, (R)‐rolipram, and (S)‐nebracetam.     

Visible-Light-Curable Solvent-Free Acrylic Pressure-Sensitive Adhesives via Photoredox-Mediated Radical Polymerization

Owing to their excellent properties, such as transparency, resistance to oxidation, and high adhesivity, acrylic pressure-sensitive adhesives (PSAs) are widely used. Recently, solvent-free acrylic PSAs, which are typically prepared via photopolymerization, have attracted increasing attention because of the current strict environmental regulations. UV light is commonly used as an excitation source for photopolymerization, whereas visible light, which is safer for humans, is rarely utilized. In this study, we prepared solvent-free acrylic PSAs via visible light-driven photoredox-mediated radical polymerization. Three α-haloesters were used as additives to overcome critical shortcomings, such as the previously reported low film curing rate and poor transparency observed during additive-free photocatalytic polymerization. The film curing rate was greatly increased in the presence of α-haloesters, which lowered the photocatalyst loadings and, hence, improved the film transparency. These results confirmed that our method could be widely used to prepare general-purpose solvent-free PSAs—in particular, optically clear adhesives for electronics.     

Visible-Light-Active Coumarin- and Quinolinone-Based Photocatalysts and Their Applications in Chemical Transformations

Organic dyes have been actively studied as useful photocatalysts because they allow access to versatile structural flexibility and green synthetic applications. The identification of a new class of robust organic chromophores is, therefore, in high demand to increase structural diversity and variability. Although coumarins and quinolinones have long been acknowledged as organic chromophores, their ability to participate in photoinduced transformations is somewhat less familiar. Fascinated by their chromophoric features and adaptable platform, our group is interested in the identification of fluorescent bioactive molecules and in the development of new photoinduced synthetic methods using coumarins and quinolinones as photocatalysts. This account provides an overview of our recent progress in the discovery and application of light-absorbing coumarin and quinolinone derivatives in photochemistry and medicinal chemistry.