Preparation and Microscopic Characterization of Asphalt Modified by Ethylene Metal-free Phthalocyanine-dispersed Graphene

Graphene-modified asphalt(GMA)for road application was prepared via using metal-free phthalocyanine-dispersed to modify an SK-70#base asphalt with graphene.The preparation parameters are as follows:the content of graphene is 0.26%based on the mass percentage of absolute ethanol,the content of nonmetal phthalocyanine is 190%based on the mass percentage of graphene,and then the GMA is prepared via unique high-speed shearing with continuing to ventilate nitrogen,which can prevent the aging of modified asphalt in the high-speed shearing process,and effectively evaluate the modifier.The penetration,softening point,force ductility,and fracture energy of GMA were significantly improved based on the base asphalt.Thus,the incorporation of graphene could enhance the base asphalt’s high-and low-temperature stability.The modification mechanism was researched via metallographic microscopy,computed tomography(CT),Fourier transform infrared spectroscopy(FTIR),and atomic force microscopy(AFM).Adsorption and physical dispersion of the asphaltenes and resins in the phthalocyanine-graphene system were confirmed.

Recent advances and perspectives of zinc metal-free anodes for zinc ion batteries

Zinc-ion batteries(ZIBs) are recognized as potential energy storage devices due to their advantages of low cost, high energy density, and environmental friendliness. However, zinc anodes are subject to unavoidable zinc dendrites, passivation, corrosion, and hydrogen evolution reactions during the charging and discharging of batteries, becoming obstacles to the practical application of ZIBs. Appropriate zinc metal-free anodes provide a higher working potential than metallic zinc anodes, effectively solving the problems of zinc dendrites, hydrogen evolution, and side reactions during the operation of metallic zinc anodes. The improvement in the safety and cycle life of batteries creates conditions for further commercialization of ZIBs. Therefore, this work systematically introduces the research progress of zinc metal-free anodes in “rocking chair” ZIBs. Zinc metal-free anodes are mainly discussed in four categories: transition metal oxides,transition metal sulfides, MXene(two dimensional transition metal carbide) composites, and organic compounds, with discussions on their properties and zinc storage mechanisms. Finally, the outlook for the development of zinc metal-free anodes is proposed. This paper is expected to provide a reference for the further promotion of commercial rechargeable ZIBs.

Recent Advances in Mechanistic Understanding of Metal-Free Carbon Thermocatalysis and Electrocatalysis with Model Molecules

Metal-free carbon,as the most representative heterogeneous metal-free catalysts,have received considerable interests in electro-and thermo-catalytic reac-tions due to their impressive performance and sustainability.Over the past decade,well-designed carbon catalysts with tunable structures and heteroatom groups coupled with various characterization techniques have proposed numerous reaction mechanisms.However,active sites,key intermediate species,precise structure-activity relationships and dynamic evolution processes of carbon catalysts are still rife with controversies due to the monotony and limitation of used experimental methods.In this Review,we sum-marize the extensive efforts on model catalysts since the 2000s,particularly in the past decade,to overcome the influences of material and structure limitations in metal-free carbon catalysis.Using both nanomolecule model and bulk model,the real contribution of each alien species,defect and edge configuration to a series of fundamentally important reactions,such as thermocatalytic reactions,electrocatalytic reactions,were systematically studied.Combined with in situ techniques,isotope labeling and size control,the detailed reaction mechanisms,the precise 2D structure-activity relationships and the rate-determining steps were revealed at a molecular level.Furthermore,the outlook of model carbon catalysis has also been proposed in this work.

Indirect Electroanalysis of 3-Methyl-4-Nitrophenol in Water Using Carbon Fiber Microelectrode Modified with Nickel Tetrasulfonated Phthalocyanine Complex

Electrochemical detection of 3-methyl-4-nitrophenol (MNP) in direct phenol oxidation occurs at high potentials and generally leads to progressive passivation of the electrochemical sensor. This study describes the use of a carbon fiber microelectrode modified with a tetrasulfonated nickel phthalocyanine complex for the detection of MNP at a lower potential than that of direct phenol oxidation. The MNP voltammogram showed the presence of an anodic peak at -0.11 V vs SCE, corresponding to the oxidation of the hydroxylamine group generated after the reduction of the nitro group. The effect of buffer pH on the peak current and SWV parameters such as frequency, scan increment, and pulse amplitude were studied and optimized to have better electrochemical response of the proposed sensor. With these optimal parameters, the calibration curve shows that the peak current varied linearly as a function of MNP concentration, leading to a limit of detection (LoD) of 1.1 μg/L. These results show an appreciable sensitivity of the sensor for detecting the MNP at relatively low potentials, making it possible to avoid passivation phenomena.

IR and Raman Vibrational Assignments for Metal-free Phthalocyanine from Density Functional B3LYP/6-31G(d) Method

Vibrational (IR and Raman) spectra for the metal-free phthalocyanine (H2Pc) have been comparatively investi-gated through experimental and theoretical methods. The frequencies and intensities were calculated at density functional B3LYP level using the 6-31G(d) basis set. The calculated vibrational frequencies were scaled by the fac-tor 0.9613 and compared with the experimental result. In the IR spectrum, the characteristic IR band at 1008 cm-1 is interpreted as C—N (pyrrole) in-plane bending vibration, in contrast with the traditional assigned NH in-plane or out-of-plane bending vibration. The band at 874 cm-1 is attributed to the isoindole deformation and aza vibration. In the Raman spectrum, the bands at 540, 566, 1310, 1340, 1425, 1448 and 1618 cm-1 are also re-interpreted. As-signments of vibrational bands in the IR and Raman spectra are given based on density functional calculations for the first time. The present work provides valuable information to the traditional empirical assignment and will be helpful for further investigation of the vibration spectra of phthalocyanine analogues and their metal complexes.

Metal-Free 2D/2D van der Waals Heterojunction Based on Covalent Organic Frameworks for Highly Efficient Solar Energy Catalysis

Covalent organic frameworks(COFs)have emerged as a kind of rising star materials in photocatalysis.However,their photocatalytic activities are restricted by the high photogenerated electron-hole pairs recombination rate.Herein,a novel metal-free 2D/2D van der Waals heterojunction,composed of a two-dimensional(2D)COF with ketoenamine linkage(TpPa-1-COF)and 2D defective hexagonal boron nitride(h-BN),is successfully constructed through in situ solvothermal method.Benefitting from the presence of VDW heterojunction,larger contact area and intimate electronic coupling can be formed between the interface of TpPa-1-COF and defective h-BN,which make contributions to promoting charge car-riers separation.The introduced defects can also endow the h-BN with porous structure,thus providing more reactive sites.Moreover,the TpPa-1-COF will undergo a structural transformation after being integrated with defective h-BN,which can enlarge the gap between the conduction band position of the h-BN and TpPa-1-COF,and suppress electron backflow,corroborated by experimental and density functional theory calculations results.Accordingly,the resulting porous h-BN/TpPa-1-COF metal-free VDW heterojunction displays out-standing solar energy catalytic activity for water splitting without co-catalysts,and the H_(2) evolution rate can reach up to 3.15 mmol g^(−1) h^(−1),which is about 67 times greater than that of pristine TpPa-1-COF,also surpassing that of state-of-the-art metal-free-based photocatalysts reported to date.In particular,it is the first work for constructing COFs-based heterojunctions with the help of h-BN,which may provide new avenue for designing highly efficient metal-free-based photocatalysts for H_(2) evolution.

Peripheral octamethyl-substituted nickel(Ⅱ)-phthalocyanine-decorated carbon-nanotube electrodes for high-performance all-solid-state flexible symmetric supercapacitors

Construction of advanced electrode materials with unique performance for supercapacitors(SCs)is essential to achieving high implementation in the commercial market.Here,we report a novel peripheral octamethyl-substituted nickel(Ⅱ)phthalocyanine(Ni Me_(2)Pc)-based nanocomposite as the electrode material of all-solid-state SCs.The highly redox-active NiMe_(2)Pc/carboxylated carbon nanotube(CNTCOOH)dendritic nanocomposite provides rapid electron/electrolyte ion-transport pathways and exhibits excellent structural stability,resulting in high-capacity activity and impressive cycling stability.The composite prepared with the optimized weight ratio of Ni Me_(2)Pc:CNT-COOH(6:10)showed the highest specific capacitance of 330.5 F g^(-1)at 0.25 A g^(-1).The constructed NiMe_(2)Pc/CNT-COOH-based all-solid-state symmetric SC device showed excellent performance with a maximum energy density of 22.8 Wh kg^(-1)and outstanding cycling stability(111.6%retained after 35,000 cycles).Moreover,flexible carbon cloth significantly enhanced the energy density of the NiMe_(2)Pc/CNT-COOH all-solid-state symmetric device to 52.1 Wh kg^(-1)with 95.4%capacitance retention after 35,000 cycles,and it could be applied to highperformance flexible electronics applications.These findings provide a novel strategy to design phthalocyanine-based electrode materials for next-generation flexible SC devices.

Sodium-Coordinated Polymeric Phthalocyanines as Stable High-Capacity Organic Anodes for Sodium-Ion Batteries

Sodium-ion batteries(SIBs)have attracted considerable interest as an alternative to lithium-ion batteries owing to their similar electrochemical performance and superior long-term cycle stability.Organic materials are regarded as promising anode materials for constructing SIBs with high capacity and good retention.However,utilization of organic materials is rather limited by their low energy density and poor stability at high current densities.To overcome these limitations,we utilized a novel polymeric disodium phthalocyanines(pNaPc)as SIB anodes to provide stable coordination sites for Na ions as well as to enhance the stability at high current density.By varying the linker type during a one-pot cyclization and polymerization process,two pNaPc anodes with O-(O-pNaPc)and S-linkers(S-pNaPc)were prepared,and their structural and electrochemical properties were investigated.The O-pNaPc binds Na ions with a lower binding energy compared with S-pNaPc,which leads to more facile Na-ion coordination/dissociation when engaged as SIB anode.The use of O-pNaPc significantly improves the redox kinetics and cycle stability and allows the fabrication of a full cell against Na_(3)V_(2)(PO_(4))_(2)F_(3)/C cathode,which demonstrates its practical application with high energy density(288 Wh kg^(-1))and high power density(149 W kg^(-1)).

Conjugated polymerized bimetallic phthalocyanine based electrocatalyst with Fe-N_(4)/Co-N_(4) dual-sites synergistic effect for zinc-air battery

The bifunctional oxygen catalyst is essential for zinc-air batteries(ZABs).Here,an efficient bifunctional oxygen catalyst,PPcFeCo/3D-G,is obtained throughπ-πinteraction between the conjugated polymerized iron-cobalt phthalocyanine(PPcFeCo)with excellent thermal stability and three-dimensional graphene(3D-G).The bimetallic synergistic effect of PPcFeCo,verified by DFT(Density functional theory)calculation,andπ-πinteractions enhances the catalytic activity and durability of the PPcFeCo/3D-G.Regarding electrochemical performance,the PPcFeCo/3D-G with a high electron transfer number(3.98,@0.768 V vs.RHE)has excellent half-wave potential(E_(1/2)=0.890 V vs.RHE)and exhibits outstanding reversibility(ΔE=0.700 V,ΔE=Ej=10-E_(1/2)).The liquid ZAB(LZAB)employed PPcFeCo/3D-G displays a high power density(222 m W cm^(-2)),a specific capacity(792 m A h g-1),and excellent durability(120 h).This work has guiding significance for the preparation of high-efficiency bifunctional catalysts.

Cobalt phthalocyanine-based conjugated polymer as efficient and exclusive electrocatalyst for CO_(2) reduction to ethanol

Electrocatalytic conversion of carbon dioxide to high value-added chemicals is a promising method for solving the energy crisis and global warming.Electrochemical active metal-containing conjugated polymers have been widely studied for heterogeneous carbon dioxide reduction.In the present contribution,we designed and synthesized a stable cobalt phthalocyanine-based conjugated polymer,named CoPPc-TFPPy-CP,and also explored its electro-catalytic application in carbon dioxide reduction to liquid products in an aqueous solution.In the catalyst,cobalt phthalocyanine acts as building blocks connected with 1,3,6,8-tetrakis(4-formyl phenyl)pyrenes via imine-linkages,leading to mesoporous formation polymers with the pore size centered at 4.1nm.And the central co-balt atoms shifted to a higher oxidation state after condensation.With these chemical and structural natures,the catalyst displayed a remarkable electrocatalytic CO_(2) reduction performance with an ethanol Faradaic efficiency of 43.25%at-1.0V vs RHE.While at the same time,the electrochemical reduction process catalyzed by cobalt phthalocyanine produced only carbon monoxide and hydrogen.To the best of our knowledge,CoPPc-TFPPy-CP is the first example among organic polymers and metal-organic frameworks that produces ethanol from CO_(2) with a remarkable selectivity.

Structure of Cu-Phthalocyanine Vacuum Deposited on Inclined Glass Substrates

Cu-phthalocyanine is widely studied as a hole-transport layer in organic electronic devices. Since Cu-phthalocyanine is a molecular solid, the crystal structure depends on a circumstance to a great extent. Vacuum deposited layers were known to consist of two consecutive layers. In this article, Cu-phthalocyanine was deposited on the glass substrate inclined at several angles. The thickness of the first layer was found to be dependent on the substrate angle.

Rational design of carbon-based metal-free catalysts for electrochemical carbon dioxide reduction: A review

Electrochemical CO2 reduction to chemicals or fuels presents one of the most promising strategies for managing the global carbon balance, which yet poses a significant challenge due to lack of efficient and durable electrocatalyst as well as the understanding of the CO2 reduction reaction(CO2RR) mechanism.Benefiting from the large surface area, high electrical conductivity, and tunable structure, carbon-based metal-free materials(CMs) have been extensively studied as cost-effective electrocatalysts for CO2RR.The development of CMs with low cost, high activity and durability for CO2RR has been considered as one of the most active and competitive directions in electrochemistry and material science.In this review article,some up-to-date strategies in improving the CO2RR performance on CMs are summarized.Specifically, the approaches to optimize the adsorption of CO2RR intermediates, such as tuning the physical and electronic structure are introduced, which can enhance the electrocatalytic activity of CMs effectively.Finally, some design strategies are proposed to prepare CMs with high activity and selectivity for CO2RR.

Study on the Synthesis and in vitro Photodynamic Anti-cancer Activity of Tetra(trifluoroethoxy) Germanium Phthalocyanine

The synthesis and in vitro photodynamic anticancer activity of a new photosen- sitizer, tetra（trifluoroethoxy） germanium phthalocyanine （GePcF）, were studied. GePcF was characterized by UV-Vis, IR, MS and elemental analysis. The in vitro photodynamic activity of GePcF was studied by MTT. IC50 of GePcF for SW480 cells of human colonic adenocarcinoma and HeLa cells of cervical cancer were 36.53 and 45.78 μmol/L, respectively. GePcF as a photosensitizer may be used to treat cancers due to its photodyrmmic anticancer activity.

Calculation of Visible Absorption Maxima of Phthalocyanine Compounds by Quantum Theory

Based on HYPERCHEM, the structures of five phthalocyanie compounds were optimized with PM3 and their visible absorption maxima were calculated with ZINDO/S method by selecting appropriate p-p overlap weighting factor (OWFp-p), the agreement with experiment was excellent. The relationship between OWF- and molecular structure parameters was obtained by the method of stepwise regression and was explained in terms of quantum theory. OWF-=0.58126+0.04562ANC1+0.03839X. Where, ANC1 and X are the symbols of average net charges on coordinated bonded nitrogens and electronegativity of central atom, respectively.

Synthesis and Photoconductivity of Nanosized Phthalocyanine

Functional phthalocyanine （Pc） compounds of H2Pc, TiOPc, FePc and CIAIPc were synthesized with a yield of 46.7%, 91.2%, 37.4% and 34.0%, respectively. Nanosized TiOPc was synthesized via a one-step sol-gel method and effects of surfactant doses, nucleation temperature on TiOPc particle size and photoconductivity were investigated. When re（PEG）： m（TiOPc） was 0.1 and nucleation temperature was 0℃, the as-obtained TiOPc had the smallest particle size and largest specific surface area, which were 60 nm and 83m^2/g, respectively. TiOPc synthesized under these conditions also exhibits excellent photoconductivity with charging potential V0, dark decay speed Rd and energy for half-discharging of potential E1/2 being 1160 V, 30 V/s and 0.6 1x.s, respectively.

Direct Growth of Graphene on Silicon by Metal-Free Chemical Vapor Deposition

The metal-free synthesis of graphene on singlecrystal silicon substrates, the most common commercial semiconductor, is of paramount significance for many technological applications. In this work, we report the growth of graphene directly on an upside-down placed,single-crystal silicon substrate using metal-free, ambientpressure chemical vapor deposition. By controlling the growth temperature, in-plane propagation, edge-propagation, and core-propagation, the process of graphene growth on silicon can be identified. This process produces atomically flat monolayer or bilayer graphene domains, concave bilayer graphene domains, and bulging few-layer graphene domains. This work would be a significant step toward the synthesis of large-area and layer-controlled, high-quality graphene on single-crystal silicon substrates.

Surface/interface engineering of high-efficiency noble metal-free electrocatalysts for energy-related electrochemical reactions

To date,much efforts have been devoted to the high-efficiency noble metal-free electrocatalysts for hydrogen-and oxygen-involving energy conversion reactions,due to their abundance,low cost and nultifunctionally.Surface/interface engineering is found to be effective in achieving novel physicochemical properties and synergistic effects in nanomaterials for electrocatalysis.Among various engineering strategies,heteroatom-doping has been regarded as a most promising method to improve the electrocatalytic performance via the regulation of electronic structure of catalysts,and numerous works were reported on the synthesis method and mechanism investigation of heteroatom-doping electrocatalysts,though the heteroatom-doping can only provide limited active sites.Engineering of other defects such as vacancies and edge sites and construction of heterostructure have shown to open up a potential avenue for the development of noble metal-free electrocatalysts.In addition,surface functionalization can attach various molecules onto the surface of materials to easily modify their physical or chemical properties,being as a promising complement or substitute for offering materials with catalytic properties.This paper gives the insights into the diverse strategies of surface/interface engineering of the highefficiency noble metal-free electrocatalysts for energy-related electrochemical reactions.The significant advances are summarized.The unique advantages and mechanisms for specific applications are highlighted.The current challenges and outlook of this growing field are also discussed.

Hexagonal boron nitride:A metal-free catalyst for deep oxidative desulfurization of fuel oils

Oxidative desulfurization(ODS)has been proved to be an efficient strategy for the production of clean fuel oil.Numerous metal-based materials have been employed as excellent ODS catalysts,but being hindered by their high-cost and potential secondary pollution.In this work,we employed graphene analogous hexagonal boron nitride(h-BN)as a metal-free catalyst for ODS with hydrogen peroxide(H2O2)as the oxidant.The h-BN catalyst was characterized and proved to be a few-layered structure with relatively high specific surface areas.The h-BN catalyst showed a 99.4%of sulfur removal in fuel oil under the optimized reaction conditions.Besides,the h-BN can be recycled for 8 times without significant decrease in the catalytic performance.Detailed mechanism analysis found that it is the boron radicals in h-BN activated H2O2 to generate·OH species,which can readily oxidize sulfides to corresponding sulfones for separation.This work would provide another choice in choosing metal-free catalysts for ODS.

Metal-free carbocatalysis for electrochemical oxygen reduction reaction: Activity origin and mechanism

Although scientists have conducted long-term and extensive studies on oxygen reduction reaction(ORR)catalyzed by metal-free carbon materials,they mainly have focused on the preparation and properties of various doped carbon materials.There is still a lack of systematic scientific guidance on the relationship between the surface structure regulation and activity of carbon-based catalysts.In this review,some of electrochemical and computational fundamental concepts about ORR are concisely summarized.The effects of edge defect and nonmetallic doping of carbon materials on ORR behavior and mechanism have been reviewed,and activity origin identification and intermediate conversion mechanism have been discussed.The outlooks for future researches on metal-free ORR electrocatalysis are suggested.

First-Principles Study of Two Dimensional Transition Metal Phthalocyanine-Based Metal-Organic Frameworks in Kagome Lattice

Transition metal phthalocyanines (TMPc) and relevant derivatives can act as pervasive molecules for their electronic, magnetic, and optical applications. Numerous researches based on TMPc are carried out, attempting to synthesize novel two-dimensional (2D) metal-organic frameworks. Recently, some 2D poly-TMPc frameworks including FePc [J. Am. Chem. Soc. 133, 1203 (2011)], CoPc [Chem. Commun. 51, 2836 (2015)], and Ni-NiPc [J. Mater. Chem. A 6, 1188 (2018)] frameworks have been successfully synthesized experimentally. Meanwhile, potential applications in catalysis, gas storage, and spintronics were predicted by theoretical studies. Here, we propose a new kind of 2D poly-TMPc frameworks with kagome lattice (denoted as kag-TMPc) and systematically investigate their electronic and magnetic properties by employing first-principles calculations. We have demonstrated that the 2D kag-MnPc framework displays quite stable ferromagnetic ordering with Curie temperature about 125 K as indicated by Monte Carlo simulations based on Heisenberg model and prefers out-of-plane easy-magnetization axis. The 2D kag-CrPc framework is an ideal candidate for S=2 kagome antiferromagnet with RT3 magnetic order. Particularly, the investigations on optical absorption suggest that when the TMPc molecules are self-assembled into 2D kag- TMPc frameworks, their absorption wave bands are broadened, especially in visible region.