Good Chemical Stability Research Articles

Y, Yb, and Gd tri-doping on B-site of Ba(Zr, Ce)O3-δ with improved proton conduction performance

Perovskite-type proton conducting electrolytes are garnering significant attention due to its key role in protonic ceramic electrochemical cells (PCEC) and its application in hydrogen sensors (HS) used for metal melt measurements. Developing high proton conduction perovskite materials with good chemical stability is always a worldwide research focus. In this paper, Y, Yb and Gd triple-doping on B-site of BaCeO3-BaZrO3 solid solution were carried out to investigate the effect of gadolinium doping on the performance of protonic conducting electrolytes. BaZr0.1Ce0.7(Y0.5Yb0.5)0.2-xGdxO3-δ (x = 0, 0.1, 0.15 and 0.2), which were also referred as BZCYYbGdx (x = 0, 10, 15 and 20), were synthesized by solid-state reaction at 1600 °C for 10 h. It is found that BZCYYbGd15 has the highest proton conductivity and proton transfer number among the four prepared materials. The proton mobility of BZCYYbGd15 is 4.06 × 10−6 cm2/(Vꞏs) at 800 °C, which increases with an increased temperature. Its proton transfer number is higher than 0.9 at 500 °C under the atmosphere of PH2O = 0.018 atm. A moderate doping of gadolinium increases the temperature threshold for proton conduction. Proton, oxygen vacancy, electron hole and total conductivity activation energies of BZCYYbGd15 under the wet atmosphere are found to be 0.74, 1.58, 1.41 and 0.92 eV, respectively. Furthermore, the chemical stability of pellets is improved after gadolinium doping. This study provides a reference value for future research on high proton conduction electrolytes.

Effect of Gd2O3 substitution for La2O3 on structure, physicochemical and electrical properties in aluminoborosilicate glasses for advanced microelectronics packaging

Currently, to develop new glass materials with lower dielectric constant (εr) and dielectric loss (tanδ), low coefficient of thermal expansion (CTE), excellent thermal stability and chemical stability for advanced microelectronics packaging has been significant pursuits of many researchers. In this work, novel 58SiO2-20B2O3-8Al2O3-10CaO-1Na2O-(3-x) La2O3-x Gd2O3 (x=0, 0.5, 1, 1.5, 2, 2.5 and 3 mol%) were successfully fabricated by the conventional melt annealing method. The results revealed that single addition of Gd2O3 or La2O3 (x=0, 3 mol%) strengthened glass network structure, which in turn improved performances of the glass. It was interestingly found that similar to the mixed-base effect, double-doped Gd2O3 and La2O3 played a greater role in improving glass structure and properties. The glass with x=1.5 mol% Gd2O3 exhibited the lowest dielectric permittivity, dielectric loss and low coefficient of thermal expansion (εr = 4.72, tanδ = 0.0004 (@1 MHz), CTE = 3.78 ppm/°C) and good chemical stability, which is optimal for the comprehensive performance compared with other aluminoborosilicate (Al-B-Si) glasses reported so far. These findings highlight that this glass is expected to be used in the microelectronics packaging field.

Design and Synthesis of Sb-Doped CuS@C Hollow Nanocubes as Efficient Anode Materials for Sodium-Ion Battery.

Copper sulfide has received widespread attention for application as anode materials in sodium-ion batteries due to their potent capabilitiess and eco-friendly properties. However, it is a challenge to achieve a high rate capability and long cycle stability owing to the heterogeneous transfer of sodium ions during charge-discharge, the interior poor electron conductivity and repeated volumetric expansion of copper sulfide. In this study, Sb-doped copper sulfide hollow nanocubes coated with carbon shells (Sb-CuS@C) was designed and constructed as anode nanomaterials in sodium-ion batteries. Thanks to the intrinsic good electron conductivity and chemical stability of carbon shells, Sb-CuS@C possesses a higher overall electron transfer as anode material, avoids agglomeration and structural destruction during the cycling. As a result, the synthesized Sb-CuS@C achieved an excellent reversible capacity of 595 mA h g-1 after 100 cycles at 0.5 A g-1 and a good rate capability of 340 mA h g-1 at a higher 10 A g-1. DFT calculations clarify that the uniformly doped Sb would act as active sodiophilic nucleation sites to help adsorbing sodium-ion during discharging and leading uniform sodium deposition. This work provides a new insight into the structural and componential modification for common transition-metal sulfides towards application as anode materials in sodium-ion battery.

Graphitic Carbon Nitride Based Semiconductors and Their Applications in the Field of Photocatalysis

An increasing number of advanced semiconductor materials have been reported with the progress of theoretical and practical researches. The graphitic carbon nitride (g-C3N4) stands out as a highly promising semiconductor photocatalyst. It is known for its visible-light reaction and good chemical stability, indicating its potential for extensive use in photocatalysis. Recently, rapid progress has been made in researching g-C3N4-based semiconductor substances in photocatalysis. Till now, a large amount of work has focused on the applications of g-C3N4 in photocatalysis. This work focuses on those researches concerning with g-C3N4-based photocatalytic substances. Their structural characteristics, synthesis techniques, and efficiency enhancement are discussed in detail. Besides, their applications in different photocatalytic reactions are also highlighted. These reactions include hydrogen production by water decomposition, degradation of organic matter, carbon dioxide reduction, and photocatalytic bactericide. This article also points out the problems and challenges in the photocatalytic performance. Meanwhile, the stability of g-C3N4 is also highlighted. It also puts forward the promising research directions of g-C3N4 in the field of photocatalysis.

A Supramolecular‐Nanocage‐Based Framework Stabilized by π‐π Stacking Interactions with Enhanced Photocatalysis

Abstractπ frameworks, defined as a type of porous supramolecular materials weaved from conjugated molecular units by π‐π stacking interactions, provide a new direction in photocatalysis. However, such examples are rarely reported. Herein, we report a supramolecular‐nanocage‐based π framework constructed from a photoactive Cu(I) complex unit. Structurally, 24 Cu(I) complex units stack together through π‐π stacking interactions, forming a truncated octahedral nanocage with sodalite topology. The inner diameter of the nanocage is 2.8 nm. By sharing four open faces, each nanocage connects with four equivalent ones, forming a 3D porous π framework (π‐2). π‐2 shows good thermal and chemical stability, which can adsorb CO2, iodine, and methyl orange molecules. More importantly, π‐2 can serve as a photocatalyst for hydrogen evolution reaction. With ultrafine Pt subnanometer particles (0.9±0.1 nm) incorporated into the nanocages as a co‐catalyst, the hydrogen evolution rate reaches a record‐high value of 524012 μmol/gPt/h in the absence of any additional photosensitizers. The high photocatalytic activity can be ascribed to the ultrafine size of the Pt particles, as well as the fast electron transfer from π‐2 to the highly active Pt upon illumination. π‐2 represents the unique stable supramolecular‐cage‐based π framework with excellent photocatalytic activity.

A Supramolecular-Nanocage-Based Framework Stabilized by π-π Stacking Interactions with Enhanced Photocatalysis.

π frameworks, defined as a type of porous supramolecular materials weaved from conjugated molecular units by π-π stacking interactions, provide a new direction in photocatalysis. However, such examples are rarely reported. Herein, we report a supramolecular-nanocage-based π framework constructed from a photoactive Cu(I) complex unit. Structurally, 24 Cu(I) complex units stack together through π-π stacking interactions, forming a truncated octahedral nanocage with sodalite topology. The inner diameter of the nanocage is 2.8 nm. By sharing four open faces, each nanocage connects with four equivalent ones, forming a 3D porous π framework (π-2). π-2 shows good thermal and chemical stability, which can adsorb CO2, iodine, and methyl orange molecules. More importantly, π-2 can serve as a photocatalyst for hydrogen evolution reaction. With ultrafine Pt subnanometer particles (0.9±0.1 nm) incorporated into the nanocages as a co-catalyst, the hydrogen evolution rate reaches a record-high value of 524012 μmol/gPt/h in the absence of any additional photosensitizers. The high photocatalytic activity can be ascribed to the ultrafine size of the Pt particles, as well as the fast electron transfer from π-2 to the highly active Pt upon illumination. π-2 represents the unique stable supramolecular-cage-based π framework with excellent photocatalytic activity.

A Stable Layered Microporous MOF Assembled with Y-O Chains for Separation of MTO Products.

Benefiting from highly tunable pore environments, some metal-organic frameworks (MOFs) have recently shown promising prospects in the separation of methanol-to-olefin (MTO) products (mainly C3H6 and C2H4). However, the "trade-off" between gas storage capacity and selectivity always results in inefficient separation. In addition, poor stability of MOFs also limits practical separation applications. Herein, we have successfully assembled a layered Y-MOF (FJI-W9) with bent diisophthalate ligands (H4L), Y-O chains, and 2-fluorobenzoic acids. As expected, FJI-W9 not only exhibits good chemical stability but also shows significant potential for C3H6/C2H4 separation. For FJI-W9, the C3H6 uptake at 298 K and 10 kPa is 63 cm3/g, and the IAST selectivity of FJI-W9 for C3H6/C2H4 (V/V = 50/50) is calculated to be 20.5. To the best of our knowledge, both C3H6 uptake and selectivity of FJI-W9 surpass most porous materials. GCMC simulation indicates that the special supramolecular binding sites in FJI-W9 have much stronger interactions with C3H6 than C2H4 molecules. More importantly, practical breakthrough experiments demonstrate that FJI-W9 can effectively separate C3H6/C2H4 (50/50) mixtures, thus obtaining high-purity C2H4 and C3H6, respectively.

Solid‐State Electrolytes for Lithium‐Air Batteries

Li‐air batteries (LABs) have attracted widespread attention due to their extremely high theoretical capacity and energy density. However, liquid LABs face safety issues such as flammability and leakage, which hinder their practical application. In comparison, solid‐state electrolytes (SSEs) possess excellent mechanical strength, good chemical stability, a wide electrochemical window, and non‐flammable characteristics, offering a feasible strategy for achieving stable and practical LABs. In this review, we will focus on the development and challenges of different kinds of SSEs, further their interfacial issues with electrodes, and finally propose strategies and outlooks for advanced solid‐state lithium‐air batteries (SSLABs). It is expected that this review will provide a systematic understanding and theoretical guidance for design of high‐performance SSLABs.

Enhanced superhydrophobicity of acrylic polyurethane coatings by femtosecond laser ablation

In recent years, superhydrophobic coatings on aircraft surfaces have garnered significant attention due to their ability to protect the surface from corrosive source like raindrops, sand, and gasoline, etc. However, to date, research on enhancing the hydrophobicity of commercial aviation coatings on aircraft Al surface is still insufficient. In the present study, the femtosecond laser ablation technique is used to texture acrylic polyurethane coatings (denoted as APU) which has been used in the aviation field to achieve a superhydrophobic surface. The relationship between micro-/nanostructures fabricated on the coatings under different laser processing parameters and the corresponding hydrophobicity was studied. The microcone-structured superhydrophobic APU surface prepared under the optimal parameters exhibited a contact angle of 151.2° and a sliding angle of 4.2°. Durability test results show that the APU surface remains at a contact angle of more than 150° after a 140° high-temperature test and 6 h acid-base solution immersion, indicating good chemical and thermal stability. The adopted femtosecond laser fabrication technology and the resultant superhydrophobic coating in the present study may have potential applications to protect aircraft parts from corrosion damage.

Exfoliated Porous Carbon Nitride by Simultaneous Oxidation-Corrosion for Photocatalytic H2O2 Production and Organic Degradation.

Graphitic carbon nitride (g-C3N4) is a fascinating material with potential applications in photocatalysis due to its good chemical stability, high thermal stability, and relative ease of synthesis. In this work, ultrathin g-C3N4 is constructed using a hybridized method, which combines the advantages of thermal and liquid-phase stripping methods. This sample can improve performance in degrading organic pollutants several times, and the highest enhancement efficiency occurs in an alkaline environment. In addition, photocatalytic production of hydrogen peroxide can be increased to 2.6 times that of the bulk sample. These improved properties are due to the increase in specific surface area, the generation of free radicals, and adsorption capacity. This work presents a one-step exfoliation method for bulk g-C3N4 for more surface-active sites and strong redox capacity.

Highly enhanced electrocatalytic OER with facile electrodeposition of MIL–53(Fe)/NiAl–LDH/NF and NiAl–LDH/MIL–53(Fe)/NF

This research investigates a new approach to improve the electrocatalytic rate of the Oxygen Evolution Reaction (OER), a key step in water electrolysis. The study focuses on two promising materials: MIL–53(Fe) and NiAl–LDH. MIL–53(Fe) offers several advantages: high catalytic activity, large surface area, and good chemical stability. NiAl–LDH is attractive due to its layered structure, tolerance to a wide range of pH levels, scalability, and cost-effectiveness. However, their limitations like low conductivity and restricted accessibility of active sites hinder their performance in water splitting applications. To address these limitations, novel composite thin films were created using a technique called layer–by–layer (LBL) electrophoretic deposition. These films, built on nickel foam (NF) substrates, included two configurations: MIL–53(Fe)/NiAl–LDH/NF and NiAl–LDH/MIL–53(Fe)/NF. The MIL-53(Fe)/NiAl-LDH/NF composite exhibited remarkable OER activity in alkaline electrolytes, requiring overpotentials of only 200, 270, and 370 mV to reach current densities of 20, 50, and 100 mA cm−2, respectively. The Tafel slope of 54.86 mVdec−1 suggests rapid reaction kinetics. Additionally, it demonstrated excellent long-term stability, lasting for at least 20 h. The success of the MIL–53(Fe)/NiAl–LDH/NF composite can be attributed to the LBL technique. This method creates a composite with a larger surface area, significantly improving OER efficiency. In contrast, the MIL–53(Fe)/NiAl–LDH/NF configuration had the opposite effect. The NF pores became blocked by the MIL–53(Fe) layer, reducing the overall surface area, hindering electron transfer, and thereby limiting oxygen production. The LBL deposition method used in this study proves its effectiveness in designing efficient electrocatalysts. This opens up possibilities for creating other multicomponent materials for energy applications. The findings provide valuable insights for future research on these promising composite materials, potentially leading to the development of cost-effective and high-performance catalysts for various electrochemical applications.

Charge separation by switching heterojunction system from Type-II to S-scheme for enhanced photocatalytic activity: Environmental detoxification and H2 production

The development of highly efficient photocatalysts is essential for harnessing solar energy for pollutant degradation and hydrogen (H2) production. This study provides a novel ternary S-scheme photocatalyst (Fe2O3/Bi2O3/g-C3N4), prepared from optimized binary 20-Bi-C via a simple electrostatic self-assembly method for the first time. Using various methods including UV–vis DRS, PL, ESR, photocurrent, Mott-Schottky, XPS, XRD, FTIR, SEM, TEM, and BET, the optical, structural, and morphological characteristics of the produced materials were fully studied. The photocatalytic performance of as-manufactured materials was evaluated through the degradation of the Ciprofloxacin (CIP) and H2 production. Under optimized conditions determined by the RSM method, a maximum CIP degradation of 97.20 % was achieved at a rate of 0.053 min−1, with the catalyst dosage: 0.44 g/l, CIP concentration: 26.07 mg/l, pH: 6.29 and Time: 63.01. The optimized heterojunction exhibited an exceptional photocatalytic H2 generation rate of 2428 μmol·g−1·h−1 within 2 h, surpassing the binary 20-Bi-C photocatalyst by 1.3 times. Furthermore, after five continuous cycles, the 5-Fe2O3/Bi-C photocatalyst showed good chemical stability and reusability, sustaining a degradation rate of over 96 % and a TOC removal of 80 %. Experiments on the identification of free radicals have demonstrated the important roles that O2−, h+, and OH species play in the photocatalytic process. The enhancement mechanism of 5-Fe2O3/Bi-C involves the successful synthesis of Fe2O3/Bi-C photocatalyst with well-aligned positions of band gap edges, enabling the facile charge transfer through S-Scheme mechanism. Furthermore, the study investigates the impact of environmental factors, including solution pH, water matrices, and the efficiency of the synthesized photocatalyst on other organic pollutants. The photocatalytic degradation behavior of CIP is predicted using LC-MS analysis. This work provides a new method for building S-scheme heterojunctions by creatively converting the type-II heterojunction system to an S-scheme by metal oxide doping.

Z-Scheme LaFeO3/Cd0.7Zn0.3S heterojunction based on 3DOM LaFeO3 perovskite for enhanced photocatalytic hydrogen activity

The narrow band gap semiconductor LaFeO3 with ABO3 perovskite structure has been deeply studied in the field of photocatalysis due to its good thermal stability, chemical stability, photoelectric properties and suitable band position. The inverse opal structure gives the material a large specific surface area and increases the adsorption area and active site of the catalyst. In this work, it is reported for the first time that perovskite LaFeO3 inverse opal was applied to photocatalytic hydrogen production. The Cd0.7Zn0.3S QDs were deposited on the skeleton wall of LaFeO3 inverse opal to construct LaFeO3/Cd0.7Zn0.3S binary heterojunction catalyst. The LaFeO3 3DOM can effectively increase the contact area with Cd0.7Zn0.3S QDs with an increase in specific surface area, and the multiple scattering effect improves the efficiency of light utilization. The introduction of Zn2+ ions regulate the band gap position of Cd0.7Zn0.3S QDs and increases the thermodynamic reduction ability of photo generated electrons. The Z-type heterojunction effect formed by LaFeO3 inverse opal and Cd0.7Zn0.3S QDs facilitates the separation and transmission of photo generated charges. The LaFeO3/Cd0.7Zn0.3S heterojunction catalysts achieved a hydrogen production performance of 277.48 μmol/g/h due to the large specific surface area of 3DOM, good light capture ability, band gap regulation of element doping, and efficient charge separation synergistic effect of heterojunction. This work provides new insights into the design and manufacture of perovskite-type 3DOM heterojunction photocatalysts.

Tailoring iron MOF/carbon nanotube composites as flow electrodes for high-performance capacitive deionization

Capacitive deionization techniques are of interest in water treatment technology due to their low cost, excellent efficiency, and environmental friendliness. Currently, metal–organic frameworks are highly impactful candidates for use as electrode materials in electrochemistry. It provides a large pore volume, good chemical stability, and a high specific surface area. Tuning metal–organic frameworks with carbon materials will have a good impact on electrode materials with increasing performance. This study shows a facile and effective strategy for arranging flow capacitive desalination technology for salt removal. The conducting network of Fe-MOF/CNTs provides rapid electron transport and offers a high diffusion length of ions. This material exhibited excellent desalination performance, with a high salt adsorption of 80.575 mg/g at 1.6 V at an initial NaCl concentration of 1000 mg/L. Overall, the facile method and fabrication strategy greatly advances water treatment applications.

Development and characterization of an asymmetrical flat microfiltration membrane based on natural phengite clay: Application as a pretreatment for raw seawater reverse osmosis desalination

The work focuses on developing a new asymmetric flat microfiltration membrane using an inexpensive geological material, natural Moroccan phengite clay. The optimal porous ceramic support was prepared by applying the paste casting method and sintering at a low temperature of 1050 °C for 2 h. Secondly, the microfiltration layer was developed by the spin coating method. The layer was then dried and sintered at 850 °C/2h. SEM analysis revealed that the morphological structure of the layer is homogeneous and free from cracks. Furthermore, the microfiltration layer has an average pore size of 1.23 μm, a thickness ranging from 30.3 μm to 31.3 μm, a water permeability of 258.1 L/h.m2.bar, and good chemical stability against corrosion. The performance of the manufactured membrane was evaluated by filtering raw seawater (RSW1 and RSW2) as a potential application for seawater pretreatment before desalination by reverse osmosis. The prepared membrane significantly reduced turbidity concentrations by 98.7 % for RSW1 and 96.8 % for RSW2. The fouling and antifouling mechanisms were also examined. Finally, the preparation cost of the phengite membrane was estimated to be 125 $/m2.

Impact of Aging on Tensile Properties of EPDM, TPV, and eco-TPV: A Comparative Study Across Diverse Environments

Abstract This study examines the effects of aging on the tensile characteristics of Ethylene Propylene Diene Monomer (EPDM), Thermoplastic Vulcanizates (TPV), and Eco-friendly Thermoplastic Vulcanizates (Eco TPV) in different conditions. The samples underwent thermal aging at a temperature of 90°C and were immersed in sulfuric acid solutions with varying concentrations (1M, 0.1M, and 0.001M) for a duration of 1000 hours at the same temperature. The findings revealed that EPDM demonstrated the maximum tensile strength and a moderate level of elongation and breakage. Furthermore, it retained substantial mechanical integrity after undergoing aging, thereby establishing it as the most resilient material among those evaluated. The thermoplastic vulcanizate (TPV) exhibited intermediate tensile strength and elongation, but experienced significant deterioration when exposed to very acidic environments while Eco TPV had lower tensile strength but good chemical stability. The stress-strain behavior and compression set tests emphasized EPDM’s exceptional durability and ability to recover elastically. The pH measurements of the immersion solutions indicated an elevation caused by the release of alkaline chemicals from the rubber components, especially in the 1M solution.

Optimum and Green Fabrication of MIL-100(Fe) for Crystal Violet Dye Removal from Aqueous Solution

MIL-100(Fe) was prepared and subsequently used to remove crystal violet dye from aqueous solutions simulating dye-containing wastewater in the environment. In the future, it is aimed that MIL-100(Fe) can be used in managing dye-containing wastewater in the environment and reducing the negative impacts it can cause. Here, MIL-100(Fe) fabrication needs to be optimized to obtain optimum process conditions, which are environmentally friendly and can produce MIL-100(Fe) with the best characteristics. This study focused on optimizing the fabrication of MIL-100(Fe), which is a type of MOF with good chemical stability, thermal stability, and flexible structure. In this study, the room-temperature fabrication of MIL-100(Fe) was established using a ligand-to-metal molar ratio of 0.95 and an acetic acid concentration of 5.1 vol% for 6.2 h. The optimum MIL-100(Fe) was tested for crystal violet removal and provided an optimum removal capacity of 182.66 ± 3.81 mg/g. Statistical approaches are used to investigate the independent parameters and their interactions contributing to MIL-100(Fe) formation.

Polyaniline nanoparticles intercalated Ti3C2 MXene reinforced waterborne epoxy nanocomposites for electromagnetic wave absorption and anticorrosion coating applications

Ti3C2 MXene (TM) has great application potential in the field of wave absorption and corrosion resistance due to its unique performance, such as high specific surface area, high electrical conductivity, excellent mechanical and good chemical stability. However, it is difficult to obtain uniformly dispersed TM in the resin matrix due to rapid agglomeration behavior. It is difficult to obtain uniformly dispersed Ti3C2 MXene (TM) in the resin matrix due to rapid agglomeration behavior. Heren, a novel method is presented to improve the corrosion protection and dispersion of TM by polymerizing polyaniline (PANI) nanoparticles between layers. The waterborne epoxy (WEP) coating with PANI-TM had high mechanical properties including impact resistance, adhesion, and flexibility and wear resistance. The PANI-TM-WEP composites can effectively absorb more than 90 % of the electromagnetic waves and demonstrate a decreased glass transition temperature of WEP from 128.0 to 107.6 ℃. Moreover, the |Z|0.01Hz value of the PANI-TM0.5 % was 1.2369 × 106 Ω·cm2, which was one order of magnitude larger than WEP coating. The high-performance anticorrosion of PANI intercalated TM coating is attributed to the synergistic effect of impermeable TM nanosheets and passivation effect of PANI. Therefore, PANI-TM is a potential choice for applications in the fields of anticorrosion and microwave absorption.

Enhanced combustion performance of Al–Zn alloys with property optimization inspired by “two-way tunneling” strategy

Fluorinated polymers (PVDF) are widely used due to their pre-ignition reaction with Al2O3 to improve the combustion of Al. In this study, a homogeneous PVDF coating layer was constructed on the surface of Al–Zn alloys by solvent evaporation, and Al-Zn@PVDF composites with “two-way tunneling” function during thermal decomposition and combustion were prepared. The constructed PVDF coating layer can react with Al2O3 to destroy the protective layer and promote the oxidation and combustion of Al–Zn from the outside to the inside. At the same time, the energy provided by the Al-Zn@PVDF during the ignition and combustion process also promotes the melting and vaporization of Zn, which achieves the rapid and full combustion of Al–Zn alloy from the inside to outside. The “ two-way tunneling” function of Al-Zn@PVDF composites significantly improves the combustion performance, resulting in a maximum combustion temperature of 1346.9 °C for Al-Zn@PVDF-40 % and a minimum combustion duration of 1.39 s for Al-Zn@PVDF-30 %, which is a significant improvement in combustion performance. The good chemical stability of PVDF also improves the hydrophobicity of Al–Zn and enhances its applicability. In conclusion, the construction of composites with “two-way tunneling” function first proposed in this study can significantly improve the thermal decomposition and combustion properties of Al–Zn, which is expected to further facilitate its application in propellants, explosives and pyrotechnics.

Photoinduced Nonadiabatic Dynamics of a Single-Walled Carbon Nanotube-Porphyrin Complex.

Single-walled carbon nanotubes (SWCNTs) have gained a lot of attention in the past few decades due to their promising optoelectronic properties. In addition, SWCNTs can form complexes that have good chemical stability and transport properties with other optical functional materials through noncovalent interactions. Elucidating the detailed mechanism of these complexes is of great significance for improving their optoelectronic properties. Nevertheless, simulating the photoinduced dynamics of these complexes accurately is rather challenging since they usually contain hundreds of atoms. To save computational efforts, most of the previous works have ignored the excitonic effects by employing nonadiabatic carrier (electron and hole) dynamics simulations. To properly consider the influence of excitonic effects on the photoinduced ultrafast processes of the SWCNT-tetraphenyl porphyrin (H2TPP) complex and to further improve the computational efficiency, we developed the nonadiabatic molecular dynamics (NAMD) method based on the extended tight binding-based simplified Tamm-Dancoff approximation (sTDA-xTB), which is applied to study the ultrafast photoinduced dynamics of the noncovalent SWCNT-porphyrin complex. In combination with statically electronic structure calculations, the present work successfully reveals the detailed microscopic mechanism of the ultrafast excitation energy transfer process of the complex. Upon local excitation on the H2TPP molecule, an ultrafast energy transfer process occurs from H2TPP (SWCNT-H2TPP*) to SWCNT (SWCNT*-H2TPP) within 10 fs. Then, two slower processes corresponding to the energy transfer from H2TPP to SWCNT and hole transfer from H2TPP to SWCNT take place in the 1 ps time scale. The sTDA-xTB-based electronic structure calculation and NAMD simulation results not only match the previous experimental observations from static and transient spectra but also provide more insights into the detailed information on the complex's photoinduced dynamics. Therefore, the sTDA-xTB-based NAMD method is a powerful theoretical tool for studying the ultrafast photoinduced dynamics in large extended systems with a large number of electronically excited states, which could be helpful for the subsequent design of SWCNT-based functional materials.