Operando HERFD-XANES and surface sensitive Δμ analyses identify the structural evolution of copper(Ⅱ) phthalocyanine for electroreduction of CO_(2)

The quantitative understanding of how atomic-level catalyst structural changes affect the reactivity of the electrochemical CO_(2)reduction reaction is challenging.Due to the complexity of catalytic systems,conventional in situ X-ray spectroscopy plays a limited role in tracing the underlying dynamic structural changes in catalysts active sites.Herein,operando high-energy resolution fluorescence-detected X-ray absorption spectroscopy was used to precisely identify the dynamic structural transformation of well-defined active sites of a representative model copper(Ⅱ)phthalocyanine catalyst which is of guiding significance in studying single-atom catalysis system.Comprehensive X-ray spectroscopy analyses,including surface sensitive△μspectra which isolates the surface changes by subtracting the disturb of bulk base and X-ray absorption near-edge structure spectroscopy simulation,were used to discover that Cu species aggregated with increasing applied potential,which is responsible for the observed evolution of C_(2)H_(4).The approach developed in this work,characterizing the active-site geometry and dynamic structural change,is a novel and powerful technique to elucidate complex catalytic mechanisms and is expected to con tribute to the rational design of highly effective catalysts.

Organic photovoltaic cells with copper(Ⅱ) tetra-methyl substituted phthalocyanine

Efficient heterojunction organic photovoltaic （OPV） cells are fabricated based on copper tetra-methyl phthalocyanine （CuMePc） as donor and fullerene （C60） as acceptor. The power conversion efficiency of CuMePc/C60 OPV cell （2.52%） is increased by 88% compared with that of the non-peripheral substituted copper phthalocyanine （CuPc）/C60 OPV cell （1.34%）. The introduction of methyl substituent leads to stronger π–π interaction of CuMePc （～ 3.5 ？） than that of CuPc （～ 3.8 ？）. The efficiency improvement is attributed to the enhanced carrier mobility of CuMePc thin film （1.1×10-3 cm2/V·s） and better film morphology by introducing methyl groups into the periphery of CuPc molecule.

Multi-polar resistance switching and memory effect in copper phthalocyanine junctions

Copper phthalocyanine junctions, fabricated by magnetron sputtering and evaporating methods, show multi-polar （unipolar and bipolar） resistance switching and the memory effect. The multi-polar resistance switching has not been observed simultaneously in one organic material before. With both electrodes being cobalt, the unipolar resistance switching is universal. The high resistance state is switched to the low resistance state when the bias reaches the set voltage. Generally, the set voltage increases with the thickness of copper phthalocyanine and decreases with increasing dwell time of bias. Moreover, the low resistance state could be switched to the high resistance state by absorbing the phonon energy. The stability of the low resistance state could be tuned by different electrodes. In Au/copper phthalocyanine/Co system, the low resistance state is far more stable, and the bipolar resistance switching is found. Temperature dependence of electrical transport measurements demonstrates that there are no obvious differences in the electrical transport mechanism before and after the resistance switching. They fit quite well with Mott variable range hopping theory. The effect of A1203 on the resistance switching is excluded by control experiments. The holes trapping and detrapping in copper phthalocyanine layer are responsible for the resistance switching, and the interfacial effect between electrodes and copper phthalocyanine layer affects the memory effect.

THE STRUCTURE OF LANGMUIR-BLODGETT FILMS OF TETRA-NONYL PHTHALOCYANINE COPPER

Langmuir-Blodgett(LB)films of tetra-nonyl phthalocyanine copper (TNPcCu)were prepared.Molecular arrangement and orientation of these films were studied in detail.LB multilayer films of TNPcCu show a very Strong x-ray diffration peak and two weak peaks which indicate that the LB films form a quasi-crystal structure which molecules are arranged orderly.IR reflection absorption spectra and polarized VIS absorption spectra not only confirm the previous result but also indicate that phthalocyanine rings orient nearly perpendicular to the substrate surface and perpendicular to the lifting direction and the side-chain segments are not preferred oriented.

Study on Alternating LB Films of Charge-Transfer Complex of Octadecyl-TCNQ and Copper Phthalocyanine Derivative

Infrared spectra of alternating LB films of octadecyl-TCNQ/CuPc are studied. Charge-transfer complexes are formed in LB films and conductance increases about three orders than that of pure CuPc LB films.

Studying the operation characteristics and structure of vertical channel copper-phthalocyanine organic semiconductor transistor

The creation of Au/CuPc/Al/CuPc/structure is a perpendicular type electricity found in the channel of organic static induction transistor. In the following we analyze transistor operation characteristics and machine structural relation. The results express that the transistor drives the voltage low and has no-saturation current-voltage characteristics. Its operation characteristics are dependant on gate bias voltage and the construction of the aluminum electrode.The vertical channel of organic static induction transistor (OSIT), with structure of Au/CuPc/Al/CuPc/Cu, has been determined. According to the test results, the relation of its operation characteristics and device structure was analyzed. The results show that this transistor has a low driving voltage and unsaturation I-V characteristics. Its operation characteristics are dependant on gate bias voltage and the structure of the aluminum electrode.

Surface Photovoltage Studies of Moisture Sensitive Characteristic of Copper Tetrasulfonato-Phthalocyanine

The surface photovoltaic characteristic of copper tetrasulfonato- phthalocyanine (CuTsPc) in water vapor was studied by surface photovoltage spectroscopy (SPS). It was found that the adsorption of water vapor caused some marvelous changes of the photovoltaic response, that is, the SPS signal diminished rapidly and even reversed; the bands were widened and displayed a bathochromic shift. The dependence of surface photovoltage on the vapor pressure indicates that the reversed signal reaches to a maximum when the vapor pressure is 4.7×102 Pa. The time response velocity, reversibility, selectivity and reproducibili-ty were examined as well. All results obtained show that CuTsPc is of great significance in the manufacture of moisture sensitive devices. In addition, the mechanism of moisture sensitivity is discussed.

Uniform lithium deposition induced by copper phthalocyanine additive for durable lithium anode in lithium-sulfur batteries

Copper phthalocyanine(CuPc)is adopted as an electrolyte additive to stabilize lithium anode for lithiumsulfur(Li-S)batteries.CuPc with a planar molecular structure and lithiophilic N-containing group,is likely to be adsorbed on the surface of Li anode to form a coating layer,which can restrict the direct contact between Li anode and solvents,and guide the uniform deposition of Li^(+)ions.The Li||Li symmetric cells demonstrate a stable cycle performance,and Li||Cu cells show high Coulombic efficiencies.In Li-S batteries,the formed stable solid-electrolyte interface(SEI)film containing copper sulfides can protect Li anode from the polysulfide corrosion and side reactions with the electrolyte,leading to the compact and smooth surface morphology of Li anode.Therefore,the Li-S batteries with CuPc additive deliver much higher capacity,better cycle performance and rate capability as compared to the one without CuPc additive.

Efficient Carbon-Based CsPbBr_3 Inorganic Perovskite Solar Cells by Using Cu-Phthalocyanine as Hole Transport Material

Metal halide perovskite solar cells(PSCs) have attracted extensive research interest for next-generation solution-processed photovoltaic devices because of their high solar-to-electric power conversion efficiency(PCE)and low fabrication cost. Although the world's best PSC successfully achieves a considerable PCE of over 20% within a very limited timeframe after intensive efforts, the stability, high cost, and up-scaling of PSCs still remain issues. Recently, inorganic perovskite material, CsPbBr_3, is emerging as a promising photo-sensitizer with excellent durability and thermal stability, but the efficiency is still embarrassing. In this work, we intend to address these issues by exploiting CsPbBr_3 as light absorber, accompanied by using Cu-phthalocyanine(CuPc) as hole transport material(HTM) and carbon as counter electrode. The optimal device acquires a decent PCE of 6.21%, over 60% higher than those of the HTM-free devices. The systematic characterization and analysis reveal a more effective charge transfer process and a suppressed charge recombination in PSCs after introducing CuPc as hole transfer layer. More importantly, our devices exhibit an outstanding durability and a promising thermal stability, making it rather meaningful in future fabrication and application of PSCs.

Photooxidation of Furfural with Phthalocyanine-sensitized TiO_2 Particle Under Xenon Lamp

Copper phthalocyanine was selected as the photosensitizer to sensitize TiO2 in this experiment with furfural as the target pollutant. The composite catalysts（TiO2/CuPC） obtained showed a great activity under a xenon lamp. By experiments, the optimal preparation conditions of the composite catalysts were set as follows ： the CuPC loading mass fraction was 1.5%, the mass fraction of acetylacetone was 0. 3% , and the stirring time was 10 h. UV-Vis diffuse reflectance spectra, XRD, and BET were used to characterize the properties of the composite catalysts, which showed that after loading CuPC on TiO2, the composite catalyst retained the same crystal structure as pure TiO2 and the wavelength range of its absorption spectrum was broadened to 600-700 nm while its surface area was smaller than that of the pure TiO2. Under the optimal conditions, 20 mg/L furfural solution was degraded by nearly 90% and TOC by about 70%. When the catalyst was reused 6 times, the activity of the catalyst was still retained by about 75%.

Identification of Dynamic Active Sites Among Cu Species Derived from MOFs@CuPc for Electrocatalytic Nitrate Reduction Reaction to Ammonia

Direct electrochemical nitrate reduction reaction(NITRR)is a promising strategy to alleviate the unbalanced nitrogen cycle while achieving the electrosynthesis of ammonia.However,the restructuration of the high-activity Cu-based electrocatalysts in the NITRR process has hindered the identification of dynamical active sites and in-depth investigation of the catalytic mechanism.Herein,Cu species(single-atom,clusters,and nanoparticles)with tunable loading supported on N-doped TiO_(2)/C are successfully manufactured with MOFs@CuPc precursors via the pre-anchor and post-pyrolysis strategy.Restructuration behavior among Cu species is co-dependent on the Cu loading and reaction potential,as evidenced by the advanced operando X-ray absorption spectroscopy,and there exists an incompletely reversible transformation of the restructured structure to the initial state.Notably,restructured CuN_(4)&Cu_(4) deliver the high NH_(3) yield of 88.2 mmol h^(−1)g_(cata)^(−1) and FE(~94.3%)at−0.75 V,resulting from the optimal adsorption of NO_(3)^(−) as well as the rapid conversion of^(*)NH_(2)OH to^(*)NH_(2) intermediates originated from the modulation of charge distribution and d-band center for Cu site.This work not only uncovers CuN_(4)&Cu_(4) have the promising NITRR but also identifies the dynamic Cu species active sites that play a critical role in the efficient electrocatalytic reduction in nitrate to ammonia.

Hyperbranched phthalocyanine enabling black-phase formamidinium perovskite solar cells processing and operating in humidity open air

The extreme instability of pureα-phase FAPbI_(3) under high humidity conditions restricts the highthroughput fabrication in unmodified air environments,resulting in poor performance ofα-phase FAPbI_(3) perovskite devices obtained by scalable fabrication methods.Here we synthesized hyperbranched copper phthalocyanine(HCuPc)as a supramolecular additive with twisted phthalocyanine units to realize the molecular-level encapsulation at the grain boundaries through supramolecular interaction,which greatly broadened the processing window of FAPbI_(3) under high humidity.At the same time,unlike traditional encapsulation layer that carrier can only be collected by tunneling effect,the twisted phthalocyanine ring of HCu Pc in perovskite films is more conducive to hole extraction.Finally,a record efficiency was achieved in pure FAPbI_(3) based inverted structured solar cell by blade-coating to the best of our knowledge,even under unmodified humid air conditions(relative humidity of 65%–85%).The best operational stability of 3D pure FAPbI_(3) devices can also be achieved at the same time and unencapsulated HCuPc-FAPbI_(3) device can even operate with negligible degradation for 100 h in the open air(RH 30%–40%).

Fabrication and Characterization of Phthalocyanine-Based Organic Solar Cells

Organic solar cells using poly (copper phthalocyanine), copper tetrakis (4-cumylphenoxy) phthalocyanine, copper phthalocyanine and titanyl phthalocyanine were fabricated and characterized. Photovoltaic properties of the solar cells with inverted structures were investigated by optical absorption, current density-voltage characteristic and incident photon to current conversion efficiency. These phthalocyanines absorbed light with wavelength longer than 500 nm. A carrier transport mechanism is proposed based on the energy level diagram.

基于CuPc-SnO_(2)复合纳米多孔材料的NO_(2)传感器研究

利用压差交换气相输运复合的方法制备CuPc-SnO_(2)复合纳米多孔材料。通过扫描电子显微镜(SEM)及附带能谱仪(EDS)和傅里叶变换红外(FTIR)光谱仪对所得样品的微观形貌及元素成分进行表征,通过气敏分析系统测试其气敏性能。结果表明:该CuPc-SnO_(2)复合气体传感器对NO_(2)气体的灵敏度响应要明显优于纯的SnO_(2),在最佳工作温度120℃,传感器灵敏度与NO_(2)气体体积分数呈较好的线性关系,且对NO_(2)气体表现出良好的选择性。此外,通过原位霍尔测试系统对可能的气敏机理进行探讨。

空穴注入型CuPc二氧化氮气体传感器研究

讨论了一种新型的基于空穴注入效应的电导型CuPc薄膜二氧化氮气体传感器,其器件结构为:采用溅射工艺的ITO(InO、ZnO)作下电极,真空蒸发CuPc薄膜作为敏感功能层,上电极为AL叉指电极。这种CuPc传感器与传统的AlO_3/CuPc/Al相比,电阻下降了3～4个数量级。同时讨论了该传感器的敏感特性。

两级A/O+铁盐耦合沉淀组合工艺处理酞菁铜生产废水

经除铜预处理后的酞菁铜生产废水含有大量难生物降解的酞菁等含氮有机物,采用传统的“生物处理+深度处理”组合工艺处理该废水时,处理效果不稳定,且出水总氮(TN)难以达标。采用“两级A/O+铁盐耦合沉淀”组合工艺处理该废水,考察其处理效果,并利用荧光光谱、紫外光谱、腐殖质(HS)含量测定探究废水中污染物的去除机理。结果表明,“两级A/O+铁盐耦合沉淀”组合工艺处理酞菁铜生产废水,化学需氧量(COD)、氨氮、TN的去除率分别为96.5%、99.8%、93.2%;两级A/O可有效去除废水中绝大部分污染物,并使出水中HS含量提高,再利用对HS和有机氮具有高效去除作用的铁盐耦合沉淀技术处理两级A/O出水,使最终出水的COD、氨氮、TN分别为29、0.5、23.8 mg/L,实现了出水达标排放。

高比表面积CuPc/TiO_2纳米管复合材料的制备及其可见光光催化活性

以P25为前驱体,在碱性条件下采用水热法制备了TiO2纳米管(NT),然后通过浸渍法将敏化剂酞菁铜(CuPc)附着于TiO2NT表面,制得可见光响应的CuPc/TiO2NT复合光催化材料,并对其进行了表征,考察了它在可见光下降解罗丹明B的光催化活性.结果表明,在NaOH碱性条件下水热法制备的TiO2NT具有较大的比表面积(362.6m2/g)和高孔容(2.039cm3/g),经0.2%CuPc修饰后,复合材料仍然保持较高的比表面积(244.2m2/g)和孔容(1.024cm3/g),进而提高了CuPc与TiO2界面的光生电荷转移速率,使光生电子-空穴能够在此界面上形成有效分离,从而明显提高了复合材料的光催化活性.在可见光辐照下,0.2%CuPc/TiO2NT复合材料的光催化性能最好,反应180min时,罗丹明B的降解率可达59%,比TiO2NT的提高了3.3倍.

CuPcTs敏化TiO_2光催化剂降解DEHP的研究

邻苯二甲酸二(2-乙基己基)酯(DEHP)是我国水环境中广泛存在的一种有机污染物,以其致畸性、致突变性、致癌性以及生殖毒性而引起广泛关注。以钛酸四丁酯为原料,四磺酸酞菁铜(CuPcTs)为敏化剂,采用水热法原位制备了CuPcTs/TiO2复合纳米光催化剂。在可见光照射下,用制备的CuPcTs/TiO2为催化剂对DEHP溶液进行了光催化降解实验,结果表明:在催化剂质量浓度为400 mg/L,pH为5,初始质量浓度为10 mg/L条件下,DEHP的降解率达到93.6%。

氮杂酞菁铜aza-CuPc的合成与晶体结构

The azaanalog of copper phthalocyanine（azaCuPc） complex C 24H 8CuN 16 was prepared by the so- lid phase synthesis technology and its single crystals was characterized by high power Xray from the synchrotron radiation. The crystal belongs to monoclinic system, space group P21/n with a=1.612 3（3） nm, b= 0.529 40（11） nm, c=1.906 4（4） nm, β=105.25（3）°, V=1.569 9（5） nm, Z=2, Mr=584.00, Dc=1.235 g/cm3, F（000）=586, the final R=0.063 1 and wR=0.153 9 for 757 observed reflections with I>2σ（I）, GOF=1.340.

超细Cu／CuPc复合粒子的制备研究

以苯酐及尿素为主要原料，固相熔融制备CuPc。在饱和CuPc磷酸溶液中，改变铜粉加入量及蒸馏水或以不同浓度的十二烷基苯磺酸钠溶液代替蒸馏水的稀释速度，使CuPc在液相中析出并沉积在铜粉表面，覆盖金属光泽，制备出蓝色的包覆完全的Cu／CuPc超细复合粒子。并对Cu／CuPc复合粒子进行SEM及XRD表征。