揭示D-A聚合物光催化剂中的超快激子分离

近年来,具有给-受体结构的有机半导体聚合物在光催化领域中取得了显著的研究进展.研究主要集中在通过分子设计,采用自下而上的方法,合成具有不同分子结构的聚合物材料.研究人员深入考察了聚合物光催化性能与其自身性质(如能带结构、形貌、吸光能力等)之间的关系.尽管这些研究为光催化领域的发展提供了重要基础,但现有研究方法仍存在一些问题,如自下而上合成路线的规模化应用困难,以及性能与结构关系研究的普适性不足.因此,未来研究需要进一步探索和改进合成方法,以及深化对光催化性能与材料结构之间关系的理解.中国地质大学(武汉)的余家国教授、张留洋教授与美国肯特州立大学的Mietek Jaroniec教授合作,采用傅克烷基化反应合成了具有给体-给体结构的聚合物.随后,通过后合成修饰,实现了该聚合物到给体-受体结构的原位光诱导转化,并系统地研究了转变前后聚合物中激子的分离过程.实验结果表明,在光照条件下,初始聚合物knitting DBT(KDBT)的结构单元二苯并噻吩(DBT)会部分氧化为二苯并噻吩-S,S-二氧化物(DBTSO),进而形成新聚合物KDBT-A,并伴随偶极矩增加和ICT态形成.瞬态技术(时间分辨荧光光谱和飞秒瞬态吸收光谱)表征结果表明,KDBT与KDBT-A中的激子都能发生解离,但KDBT-A中的激子解离速率要远快于KDBT.这表明ICT态的形成有效抑制了激子复合.因此,随着聚合物结构从给体-给体结构转变为给体-受体结构,其光催化活性得到了显著增强.综上,这种光诱导原位改变分子结构的方法不仅能促进给体-受体型聚合物光催化剂的发展,还为有机太阳能电池、有机发光二极管、传感器等多个领域的研究提供新策略.

利用飞秒技术研究电荷转移动力学

光催化材料和技术可合理利用太阳能,完成能量转化与存储,并实现环境治理和双碳目标.光催化剂活性是影响其效率的关键,因此光催化剂的合理设计成为研究热点.为抑制光生电子和空穴的快速复合并拓展单一光催化剂的光吸收范围,可通过构建异质结特别是新兴的梯型(S型异质结)的策略.在保有体系最大氧化还原能力的同时,实现光生电荷的有效分离.可通过原位光照X射线光电子能谱和原位光照原子力显微镜等技术研究梯型异质结的电荷转移机制,然而,目前尚缺少对于异质结界面处瞬态动力学的深入研究.近期,中国地质大学(武汉)余家国教授、张留洋教授与湖北文理学院梁桂杰教授合作,通过原位生长策略,在芘基共轭聚合物(PDB)表面原位生长硫化镉(Cd S)纳米晶体,制备了一系列硫化镉/聚合物梯型异质结(CPDB),并系统地研究了异质结界面处的稳态电荷分布以及瞬态电荷转移动力学.密度泛函理论计算和开尔文探针测试结果表明,暗态下电子由PDB向Cd S转移,并在界面处形成内建电场和能带弯曲.原位光照X射线光电子能谱表明,在内建电场和能带弯曲的驱动下,Cd S的光生电子与PDB的光生空穴复合,而PDB的光生电子与Cd S的光生空穴得以保留.利用飞秒瞬态吸收技术揭示了异质结界面处的电荷转移演化过程.通过实验信号的拟合分析,Cd S的光生电子有三条衰减路径:晶格间的电子扩散、光生电子空穴对直接复合以及光生电子与捕获态空穴复合.对于CPDB复合物而言,除了上述三种衰减路径,还发现Cd S的光生电子与PDB的光生空穴复合路径.作者通过调控Cd S/PDB配比,阐述了异质结界面电荷转移过程动力学与其光催化性能的关系.结果表明,随着PDB含量的增加,Cd S与PDB之间界面电荷转移寿命越短(速度越快);然而,加入过量PDB会导致聚合物发生聚集,从而抑制界面电荷转移.该结论与CPDB复合物的光催化性能表现一致.综上,该工作通过使用飞秒瞬态吸收技术,对梯型异质结光催化剂的界面电荷转移过程进行了直接跟踪观测,为揭示光催化过程中的复杂机制提供了新思路.

Effect of preparation method on halloysite supported cobalt catalysts for Fischer-Tropsch synthesis

Novel cobalt Fischer-Tropsch synthesis （FTS） catalysts were prepared from natural halloysite nanotubes （HNT） by double-solvent and wet- impregnation methods, and characterized by TEM, XRD, TPR and N2 adsorption-desorption. Comparing with the catalyst prepared by wet- impregnation method, the catalyst prepared by double-solvent method reduces Co3O4 particle migration and agglomeration due to size-induced effect, thus showing higher catalytic activity for Fischer-Tropsch synthesis.

Carbon coated LaFe_(0.92)Pd_(0.08)O_(3) composites for catalytic transfer hydrogenation:Balance in the ability of substrates adsorption and conversion

Catalytic transfer hydrogenation(CTH)is a green and efficient pathway for selective hydrogenation of unsaturated aldehydes and ketones.However,managing the abilities of solid catalysts to adsorb substrates and to convert them into desired products is a challenging task.Herein,we report the synthesis of carbon coated LaFe_(0.92)Pd_(0.08)O_(3) composites(LFPO-8@C)for CTH of benzaldehyde(BzH)into benzyl alcohol(BzOH),using isopropanol(IPA)as hydrogen source.The coating with carbon improves the ability to adsorb/transfer reactants from solution to active sites,and the doping of Pd2+at Fe3+site strengthens the ability of LaFeO_(3) to convert BzH into BzOH.A balanced point between them(i.e.,abilities to adsorb BzH and to convert BzH into BzOH)is obtained at LFPO-8@C,which exhibits a BzOH formation rate of 3.88 mmol·gcat^(-1)·h^(-1) at 180℃ for 3 h,which is 1.50 and 2.72 times faster than those of LFPO-8 and LaFeO_(3)@C.A reaction mechanism is proposed,in which the acidic sites(e.g.,Fe^(4+),oxygen vacancy)are used for the activation of C=O bond of BzH and O-H bond of IPA,and the basic sites(e.g.,lattice oxygen)for the activation ofα-H(O-H)bond of IPA.

Electrocatalytic synthesis of C-N coupling compounds from CO_(2) and nitrogenous species

The electrocatalytic synthesis of C-N coupling compounds from CO_(2) and nitrogenous species not only offers an effective avenue to achieve carbon neutral-ity and reduce environmental pollution,but also establishes a route to synthesize valuable chemicals,such as urea,amide,and amine.This innovative approach expands the application range and product categories beyond simple carbona-ceous species in electrocatalytic CO_(2) reduction,which is becoming a rapidly advancing field.This review summarizes the research progress in electrocatalytic urea synthesis,using N_(2),NO_(2)^(-),and NO_(3)^(-)as nitrogenous species,and explores emerging trends in the electrosynthesis of amide and amine from CO_(2) and nitro-gen species.Additionally,the future opportunities in this field are highlighted,including electrosynthesis of amino acids and other compounds containing C-N bonds,anodic C-N coupling reactions beyond water oxidation,and the catalytic mechanism of corresponding reactions.This critical review also captures the insights aimed at accelerating the development of electrochemical C-N coupling reactions,confirming the superiority of this electrochemical method over the traditional techniques.

CdS/LaFeO_(3) heterojunctions with improved optical properties for visible-light catalytic applications

Construction of heterojunctions is a normal and effective strategy to improve the photocatalytic performances of semiconductors,through which both the lifetime and the redox ability of electrons/holes can be improved,as co mpared to the respective component.On this basis,we constructed Z-scheme CdS/LaFeO_(3) heterojunctions(CdS/LFO),by in-situ growing different amounts of CdS on the surface of LaFeO_(3),for photocatalytic degradation of tetracycline hydrochloride(TC)in aqueous solution at room temperature.The crystal structure,surface morphology and optoelectronic properties of the COS/LFO heterojunctions were systemically characterized to correlate the reaction activity.Photocatalytic tests indicate that the CdS/LFO heterojunctions exhibit promising activity for TC degradation under visible light irradiation(λ≥420 nm),with 85%TC conversion obtained at reaction time of 45 min,which is 3.4 and 1.9 times higher than that of CdS and LaFeO_(3).The CdS/LFO heterojunctions are also stable in the reaction and can be reused for four cycles with no appreciable activity loss.The applicability of CdS/LFO to photocatalytic degradation of organic dyes,as well as the reaction mechanism,was also explored.

Microseismic observations reveal that internal waves intensify seabed methane release

Internal waves transport material and energy from the upper water column to the deep ocean, disturbing seabed sediments and resulting in phenomena such as seabed erosion and changes in topography. On the northern slope of the South China Sea and in many coastal margins worldwide, the zones with internal wave action closely overlap with areas where natural gas hydrates are present. However, due to significant differences in the spatial and temporal scales, understanding the influence of internal waves on methane releases from deep seabeds is challenging. In this study, in situ observations of seabed microseismicity and internal waves are conducted at water depths of 655 meters and 1450 meters in the Pearl River Canyon of the South China Sea. The microseismicity caused by internal waves and seabed methane releases is identified, and a method to establish the correlation between internal waves and seabed methane releases through the use of microseismic recordings is proposed, aiming to obtain direct observational evidence of internal waves intensifying seabed methane releases. The results show that internal waves and seabed methane releases generate significant microseismic signals, indicating the continuous influence of internal waves on the deep seabed of the northern slope of the South China Sea and revealing active methane release phenomena on the seabed. At both long and short time scales, internal waves increase the frequency of seabed methane releases by 4.2 times and 2.4 times, respectively, while also enhancing the intensity of these releases. These changes are influenced by the alterations in seabed flow velocity, pressure, and temperature that are induced by internal wave activities. This study emphasizes that microseismic signals are effective carriers of information for multiscale geological processes on seabeds and suggests that internal waves exacerbate marine geological hazards and contribute to global climate change by intensifying seabed methane releases.

Effect of preparation method on physicochemical properties and catalytic performances of LaCoO3 perovskite for CO oxidation

Perovskite oxides LaCoO3 prepared by templating,co-precipitation and sol-gel method with different complexants were systematically characterized and its catalytic performances for CO oxidation were investigated.The samples were characterized by X-ray diffraction,thermogravimetry analysis and differential scanning calorimetry,N2 physisorption,transmission electron microscopy,temperature program reduction of hydrogen,temperature program desorption of oxygen and X-ray photoelectron spectroscopy measurement,results of which show that the properties of LaCoO3,such as surface morphology,surface area,surface compositions,redox capability,oxygen vacancy,as well as the calcination temperature and formation mechanism,depend intimately on the preparation method.Catalytic tests indicate that the sample prepared by carbon templating method shows the best activity for CO oxidation,with full CO conversion obtained at 135℃.In particular,the catalyst can be activated and significant increase of activity can be obtained with the increase of reaction time.The cyclic and longterm stability of catalysts were discussed and compared.

Cooperative effect between copper species and oxygen vacancy in Ce_(0.7−x)Zr_(x)Cu_(0.3)O_(2) catalysts for carbon monoxide oxidation

The effects of Zr doping on the existence of Cu and the catalytic performance of Ce_(0.7−x)Zr_(x)Cu_(0.3)O_(2)for CO oxidation were investigated.The characterization results showed that all samples have a cubic structure,and a small amount of Zr doping facilitates Cu^(2+) ions entering the CeO2 lattice,but excessive Zr doping leads to the formation of surface CuO crystals again.Thus,the number of oxygen vacancies caused by the Cu^(2+) entering the lattice(e.g.,Cu^(2+)-□-Ce^(4+);□:oxygen vacancy),and the amount of reducible copper species caused by CuO crystals,varies with the Zr doping.Catalytic CO oxidation tests indicated that the oxygen vacancy and the reducible copper species were the adsorption and activation sites of O_(2)and CO,respectively,and the cooperative effects between them accounted for the high CO oxidation activity.Thus,the samples x=0.1 and 0.3,which possessed the most oxygen vacancy or reducible copper species,showed the best activity for CO oxidation,with full CO conversion obtained at 110℃.The catalyst is also stable and has good resistance to water during the reaction.

Catalytic combustion of volatile organic compounds using perovskite oxides catalysts—a review

With the rapid development of industry,volatile organic compounds(VOCs)are gaining attention as a class of pollutants that need to be eliminated due to their adverse effects on the environment and human health.Catalytic combustion is the most popular technology used for the removal of VOCs as it can be adapted to different organic emissions under mild conditions.This review first introduces the hazards of VOCs,their treatment technologies,and summarizes the treatment mechanism issues.Next,the characteristics and catalytic performance of perovskite oxides as catalysts for VOC removal are expounded,with a special focus on lattice distortions and surface defects caused by metal doping and surface modifications,and on the treatment of different VOCs.The challenges and the prospects regarding the design of perovskite oxides catalysts for the catalytic combustion of VOCs are also discussed.This review provides a reference base for improving the performance of perovskite catalysts to treat VOCs.

Photocatalytic degradation of sulfadiazine in suspensions of TiO_(2)nanosheets with exposed(001)facets

Antibiotics such as sulfonamides are widely used in agriculture as growth promoters and medicine in treatment of infectious diseases.However,the release of these antibiotics has caused serious environmental problems.In this paper,photocatalytic oxidation technology was used to degrade sulfadiazine(SDZ),one of the typical sulfonamides antibiotics,in UV illuminated TiO_(2)suspensions.It was found that TiO_(2)nanosheets(TiO_(2)-NSs)with exposed(001)facets exhibit much higher photoreactivity towards SDZ degradation compared to TiO_(2)nanoparticles(TiO_(2)-NPs)with a rate constant increases from0.017 min^(-1)to 0.035 min^(-1),improving by a factor of 2.1.Under the attacking of reactive oxygen species(ROSs)such as superoxide radicals(*O_(2)^(-))and hydroxyl radicals(*OH),SDZ was steady degraded on the surface of TiO_(2)-NSs.Based on the identification of the produced intermediates by LC–MS/MS,possible degradation pathways of SDZ,which include desulfonation,oxidation and cleavage,were put forwards.After UV irradiation for 4 h,nearly 90%of the total organic carbon(TOC)can be removed in suspensions of TiO_(2)-NSs,indicating the mineralization of SDZ.TiO_(2)-NSs also exhibits excellent stability in photocatalytic degradation of SDZ in wide range of pH.Even after recycling used for 7 times,more than 91.3%of the SDZ can be efficiently removed,indicating that they are promising to be practically used in treatment of wastewater containing antibiotics.