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Conventional Al-air battery has many disadvantages for miniwatt applications, such as the complex water management, bulky electrolyte storage and potential leakage hazard. Moreover, the self-corrosion of Al anode continues even when the electrolyte flow is stopped, leading to great Al waste. To tackle these issues, an innovative cotton-based aluminum-air battery is developed in this study. Instead of flowing alkaline solution, cotton substrate pre-deposited with solid alkaline is used, together with a small water reservoir to continuously wet the cotton and dissolve the alkaline in-situ. In this manner, the battery can be mechanically recharged by replacing the cotton substrate and refilling the water reservoir, while the thick aluminum anode can be reused for tens of times until complete consumption. The cotton substrate shows excellent ability for the storage and transportation of alkaline electrolyte, leading to a high peak power density of 73 mW cm−2 and a high specific energy of 930 mW h g−1. Moreover, the battery discharge capacity is found to be linear to the loading of pre-deposited alkaline, so that it can be precisely controlled according to the mission profile to avoid Al waste. Finally, a two-cell battery pack with common water reservoir is developed, which can provide a voltage of 2.7 V and a power output of 223.8 mW. With further scaling-up and stacking, this cotton-based Al-air battery system with low cost and high energy density is very promising for recharging miniwatt electronics in the outdoor environment.

Atmospheric CO2 concentrations are soaring due to the continued use of fossil fuels in energy production, an anthropogenic activity that is playing a leading role in global warming. Thus, research aimed at the capture and conversion of CO2 into value-added products, such as cyclic carbonates, is booming. While CO2 is an abundant, cheap, non-toxic, and readily accessible C1 feedstock, its thermodynamic stability necessitates the development of highly efficient catalysts that are able to promote chemical reactions under mild conditions. In this work, a novel mesoporous poly(ionic liquid) with dual active sites was synthesized through a facile method that involves co-polymerization, post-synthetic metalation, and supercritical CO2 drying. Due to a high density of nucleophilic and electrophilic sites, the as-prepared poly(ionic liquid), denoted as P2D-4BrBQA-Zn, offers excellent performance in a CO2 cycloaddition reaction using epichlorohydrin as the substrate (98.9% conversion and 96.9% selectivity). Moreover the reaction is carried out under mild, solvent-free, and additive-free conditions. Notably, P2D-4BrBQA-Zn also efficiently promotes the conversion of various other epoxide substrates into cyclic carbonates. Overall, the catalyst is found to have excellent substrate compatibility, stability, and recyclability.

Electrochemical CO2 reduction (CO2RR) over molecular catalysts is a paramount approach for CO2 conversion to CO. Herein, we report a novel phthalocyanine-derived catalyst synthesized by a two-step method with a much improved electroconductivity. Furthermore, the catalyst contains both Ni–N4 sites and highly dispersed metallic Ni nanoclusters, leading to an increased CO2RR currents by two folds. Isotope labelling study and in situ spectroscopic analysis demonstrate that the existence of metallic Ni nanoclusters is the key factor for the activity enhancement and can shift the CO2RR mechanism from being electron transfer (ET)-limited (forming ∗COO−) to concerted proton-electron transfer (CPET)-limited (forming CO).

In the conversion process of syngas-to-C2 species, the OH species are inevitably produced accompanying the production of key intermediates CHx(x = 1–3), traditionally, the function of surface OH species is generally accepted as the hydrogenating reactive species. This work for the first time proposed and confirmed the assisted catalytic mechanism of surface OH species that performed as the promoter for syngas-to-C2 species on Cu-based catalysts. DFT and microkinetic modeling results reveal that the produced OH species accompanying the intermediates CHx production on the MCu (M = Co, Fe, Rh) catalysts can stably exist to form OH/MCu catalysts, on which the presence of surface OH species as the promoter not only presented better activity and selectivity toward CHx(x = 1–3) compared to MCu catalysts, but also significantly suppressed CH3OH production, providing enough CHx sources to favor the production of C2 hydrocarbons and oxygenates. Correspondingly, the electronic properties analysis revealed the essential relationship between the electronic feature of OH/MCu catalysts and catalytic performance, attributing to the unique electronic micro−environment of the catalysts under the interaction of surface OH species. This new mechanism is called as OH-assisted catalytic mechanism, which may be applied in the reaction systems related to the generation of OH species.

Synthesizing nitrogen (N)-containing molecules from biomass derivatives is a new strategy for production of this kind of chemicals. Herein, for the first time we present the synthesis of N-substituted aryl pyrroles via reductive amination/cyclization of levulinic acid (LA) with primary aromatic amines and hydrosilanes (e.g., PMHS) over CsF, and a series of N-substituted aryl pyrroles could be obtained in good to excellent yields at 120 °C. The mechanism investigation indicates that the reaction proceeds in two steps: the cyclization between amine and LA occurs first to form intermediate 5-methyl-N-alkyl-1,3-dihydro-2H-pyrrolones and their isomeride (B), and then the chemo- and region-selective reduction of intermediates take place to produce the final products. This approach for synthesis of N-substituted aryl pyrroles can be performed under mild and green conditions, which may have promising applications.

Effective and robust electrocatalysts are mainly based on innovative materials and unique structures. Herein, we designed a flakelike cobalt phosphide-based catalyst supporting on NiCo2O4 nanorods array, which in-situ grew on the nickel foam (NF) current collector, referring as N–Co2P/NiCo2O4/NF electrode. By optimizing the microstructure and electronic structure through 3D hierarchy fabrication and nitrogen doping, the catalyst features with abundant electrochemical surface area, favorable surface wettability, excellent electron transport, as well as tailored d band center. Consequently, the as-prepared N–Co2P/NiCo2O4/NF electrode exhibits an impressive HER activity with a low overpotentials of 58 mV at 10 mA cm−2, a Tafel slop of 75 mV dec−1, as well as superior durability in alkaline medium. This work may provide a new pathway to effectively improve the hydrogen evolution performance of transition metal phosphides and to develop promising electrodes for practical electrocatalysis.

This work includes fabrication and electrical characterization of Metal/Interlayer/Semiconductor (MIS) structures with methyl violet organic film on p-InP wafer. Metal(Ag)/ Interlayer (methyl violet =MV)/Semiconductor(p-InP) MIS structure presents a rectifying contact behavior. The values of ideality factor (n) and barrier height (BH) for the Ag/MV/p-InP MIS diode by using the current-voltage (I-V) measurement have been extracted as 1.21 and 0.84 eV, respectively. It was seen that the BH value of 0.84 eV calculated for the Ag/MV/p-InP MIS structure was significantly higher than the value of 0.64 eV of Ag/p-InP control contact. This situation was ascribed to the fact that the MV organic interlayer increased the effective barrier height by influencing the space charge region of inorganic semiconductor. The values of diffusion potential and barrier height for the Ag/MV/p-InP MIS diode by using the capacitance-voltage (C-V) measurement have been extracted as 1.21 V and 0.84 eV, respectively. The interface-state density of the Ag/MV/p-InP structure was seen to change from 2.57×1013 eV-1cm-2 to 2.19×1012 eV-1cm-2.

Owing to the advantages of high operating voltage, environmental benignity, and low cost, potassium-based dual-ion batteries (KDIBs) have been considered as a potential candidate for large-scale energy storage. However, KDIBs generally suffer from poor cycling performance and unsatisfied capacity, and inactive components of conductive agents, binders, and current collector further lower their overall capacity. Herein, we prepare coral-like carbon nanowires (CCNWs) doped with nitrogen as a binder-free anode material for K+-ion storage, in which the unique coral-like porous nanostructure and amorphous/short-range-ordered composite feature are conducive to enhancing the structural stability, to facilitating the ion transfer and to boosting the full utilization of active sites during potassiation/de-potassiation process. As a result, the CCNW anode possesses a hybrid K+-storage mechanism of diffusive behavior and capacitive adsorption, and stably delivers a high capacity of 276 mAh g-1 at 50 mA g-1, good rate capability up to 2 A g-1, and long-term cycling stability with 93 % capacity retention after 2000 cycles at 1 A g-1. Further, assembling this CCNW anode with an environmentally benign expanded graphite (EG) cathode yields a proof-of-concept KDIB, which shows a high specific capacity of 134.4 mAh g-1 at 100 mA g-1, excellent rate capability of 106.5 mAh g-1 at 1 A g-1, and long-term cycling stability over 1000 cycles without negligible capacity loss. This study provides a feasible approach to developing high-performance anodes for potassium-based energy storage devices.

Co–N–C is a promising oxygen electrochemical catalyst due to its high stability and good durability. However, due to the limited adsorption ability improvement for oxygen-containing intermediates, it usually exhibits inadequate catalytic activity with 2-electron pathway and high selectivity of hydrogen peroxide. Herein, the adsorption of Co–N–C to these intermediates is modulated by constructing heterostructures using transition metals and their derivatives based on d-band theory. The heterostructured nanobelts with MoC core and pomegranate-like carbon shell consisting of Co nanoparticles and N dopant (MoC/Co–N–C) are engineered to successfully modulate the d band center of active Co–N–C sites, resulting in a remarkably enhanced electrocatalysis performance. The optimally performing MoC/Co–N–C exhibits outstanding bi-catalytic activity and stability for the oxygen electrochemistry, featuring a high wave-half potential of 0.865 V for the oxygen reduction reaction (ORR) and low overpotential of 370 mV for the oxygen evolution reaction (OER) at 10 mA cm−2. The zinc air batteries with the MoC/Co–N–C catalyst demonstrate a large power density of 180 mW cm−2 and a long cycling lifespan (2000 cycles). The density functional theory calculations with Hubbard correction (DFT + U) reveal the electron transferring from Co to Mo atoms that effectively modulate the d band center of the active Co sites and achieve optimum adsorption ability with “single site double adsorption” mode.

Plasma methods are given significant attention in the context of conditioning the producer gas derived from biomass gasification. The goal of this work is to present the impact of hydrogen on the other producer gas compounds during microwave plasma valorization. These compounds include main producer gas components (CO, CO2, CH4, N2) and minor impurities (tar compounds, H2S and NH3). The results prove a beneficial impact of hydrogen addition on the conversion of CH4 and toluene, increasing it from ca. 68%–95% and ca. 97%–100%, respectively. Additionally, the presence of hydrogen changes the distribution of the products, inhibiting soot and aromatics production and promoting C2 compounds. In the case of CO2, the conversion increases from ca. 18%–63% when compared to nitrogen plasma, with CO being the resulting product. The presence of hydrogen inhibits H2S conversion and does not affect CO and NH3

In molecular communications, the direct detection of signaling molecules may be challenging due to a lack of suitable sensors and interference in the environment. Motivated by research in molecular biology, we investigate an indirect detection mechanism using chemical reactions between the signaling molecules and a molecular probe to produce an easy-to-measure product at the receiver. We consider two implementations of the proposed detection mechanism, i.e., unrestricted probe movement and probes restricted to a volume around the receiver. The reaction-diffusion equations describing the concentrations of the reactant and product molecules in the system are non-linear and coupled, and cannot be solved in closed form. Therefore, we develop an efficient iterative algorithm by discretizing the time variable and solving for the space variables of the equations in each time step. Our results show that the concentrations of the product molecules and the signalling molecules share a similar characteristic over time, i.e., a single peak and a long tail. The peak and tail values of the product molecule concentration can be controlled by choosing probes with suitable parameters. By carefully choosing the molecular probe and optimizing the decision threshold, the BER can be improved significantly and outperform that of a direct detection system., 13 pages, 11 figures, 1 table. This journal version was submitted in April 2022 to the IEEE for possible publication. A part of this article was presented at the IEEE Wireless Communications and Networking Conference 2020 and stored in the previous version on arXiv

A series of CoPd/KIT-6 bimetallic catalysts with various Co:Pd molar ratios at different calcination temperatures were prepared and used for the direct synthesis of H2O2 from H2 and O2. These catalysts were characterized by nitrogen adsorption-desorption, low and wide-angle X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), elemental mapping and energy-dispersive X-ray (EDX) methods. It was found that the particle size, electronic interactions, morphology, and textural properties of these catalysts as well as their catalytic activity in the reaction of H2 with O2 were affected by Co addition and different calcination temperatures. Also, the results showed that while the H2O2 selectivity depends on Pd2+ species, the H2 conversion is related to Pd0 active sites. Among these catalysts, CoPd/KIT-6 calcined at 350 °C (CoPd/KIT-350 catalyst) showed the best catalytic activity with 50 % of H2O2 selectivity and 51 % conversion of H2.

In this work, Ag/Bi5O7I nanocomposite was prepared and firstly applied in piezo/photocatalytic reduction of N2 to NH3 and methyl orange (MO) degradation. Bi5O7I was synthesized via a hydrothermal-calcination method and shows nanorods morphology. Ag nanoparticles (NPs) were photo deposited on the Bi5O7I nanorods as electron trappers to improve the spatial separation of charge carriers, which was confirmed via XPS, TEM, and electronic chemical analyses. The catalytic test indicates that Bi5O7I presents the piezoelectric-like behavior, while the loading of Ag NPs can strengthen the character. Under ultrasonic vibration, the optimal Ag/Bi5O7I presents high efficiency in MO degradation. The degradation rate is determined to be 0.033 min−1, which is 4.7 folds faster than that of Bi5O7I. The Ag/Bi5O7I also presents a high performance in piezocatalytic N2 fixation. The piezocatalytic NH3 generation rate reaches 65.4 μmol L−1 g−1 h−1 with water as a hole scavenger. The addition of methanol can hasten the piezoelectric catalytic reaction. Interestingly, when ultrasonic vibration and light irradiation simultaneously act on the Ag/Bi5O7I catalyst, higher performance in NH3 generation and MO degradation is observed. However, due to the weak adhesion of Ag NPs, some Ag NPs would fall off from the Bi5O7I surface under long-term ultrasonic vibration, which would greatly reduce the piezoelectric catalytic performance. This result indicates that a strong binding force is required when preparing the piezoelectric composite catalyst. The current work provides new insights for the development of highly efficient catalysts that can use multiple energies.

Defect-engineered carbon materials have been emerged as promising electrocatalysts for oxygen reduction reaction (ORR) in metal-air batteries. Developing a facile strategy for the preparation of highly active nanocarbon electrocatalysts remains challenging. Herein, a low-cost and simple route is developed to synthesize defective graphene by pyrolyzing the mixture of glucose and carbon nitride. Molecular dynamics simulations reveal that the graphene formation is ascribed to two-dimensional layered feature of carbon nitride, and high compatibility of carbon nitride/glucose systems. Structural measurements suggest that the graphene possesses rich edge and topological defects. The graphene catalyst exhibits higher power density than commercial Pt/C catalyst in a primary Zn-air battery. Combining experimental results and theoretical thermodynamic analysis, it is identified that graphitic nitrogen-modified topological defects at carbon framework edges are responsible for the decent ORR performance. The strategy presented in this work can be can be scaled up readily to fabricate defective carbon materials.

Synthesizing ring structure aviation fuels from biomass-derived platform molecules is challenging, especially for bridged ring structure aviation fuels which are typically achieved from fossil-derived chemicals. Herein, we report the synthesis of a series of ring structure biofuels in two steps by a combination of a solvent-free Michael-cyclization reaction and a hydrodeoxygenation (HDO) reaction from lignocellulose-derived 5,5-dimethyl-1,3-cyclohexanedione. These biofuels are obtained with high overall yields up to 90%, which exhibit high densities of 0.81 g cm−3-0.88 g cm−3 and high volumetric neat heat of combustion (VNHOC) values of 36.0 MJ L−1-38.6 MJ L−1. More importantly, bridged-ring structure hydrocarbons can also be achieved in two steps by a combination of a Robinson annulation reaction and an HDO reaction to afford the final products at high overall yields up to 90%. The bridged-ring structure products have comparable high densities and high VNHOC values to the best artificial fuel JP-10 (0.94 g cm−3 and 39.6 MJ L−1). The results demonstrate a promising way for the synthesis of high-density aviation fuels with different fuel properties at high yields.

3D flower-like hierarchical mesoporous Bi4O5I2/MoS2 Z-scheme layered heterojunction photocatalyst was fabricated by oil bath and hydrothermal methods. The heterojunction with narrow band gap of ∼1.95 eV extended the photoresponse to near-infrared region, which showed obvious photothermal effect due to the introduction of MoS2 with broad spectrum response. MoS2 nanosheets were anchored onto the surface of flower-like hierarchical mesoporous Bi4O5I2 nanosheets, thereby forming efficient layered heterojunctions, the solar-driven photocatalytic efficiency in degradation of highly toxic dichlorophenol and reduction of hexavalent chromium was improved to 98.5% and 99.2%, which was ∼4 and 7 times higher than that of the pristine Bi4O5I2, respectively. In addition, the photocatalytic hydrogen production rate reached 496.78 μmol h-1 g-1, which was ∼6 times higher than that of the pristine Bi4O5I2. The excellent photocatalytic performance can be ascribed to the promoted photothermal effect, as well as, the formation of compact Z-scheme layered heterojunctions. The 3D flower-like hierarchical mesoporous structure provided adequate surface active-sites, which was conducive to the mass transfer. Moreover, the high stability of the prepared photocatalyst further promoted its potential practical application. This strategy also provides new insights for fabricating layered Z-scheme heterojunctions photocatalysts with highly photothermal-photocatalytic efficiency.

The Ru-catalyzed carbonylation of alkenes with CO2 as a C1 surrogate and imidazole chlorides as the promotor is investigated by a combination of computational and experimental study. The conversion rate of CO2 to CO is positively correlated with the efficiency of both hydroesterification and hydroformylation, which is found facilitated in the presence of chloride additives with a decreasing order of BmimCl ∼ B3MimCl > BmmimCl ∼ LiCl. Taking the hydroesterification with MeOH as a representative example, BmimCl bearing C–H functionality at the C2 site of the cation assists the reduction of CO2 to CO as a hydrogen donor medium, with the anion and cation acting in a synergistic fashion. Subsequent insertion of CO2 into the formed Ru–H bond with the assistance of chloride anion produces the Ru–COOH species, which ultimately accelerates the activation of CO2.

Energy conversion technologies like fuel cells and metal-air batteries require oxygen reduction reaction (ORR) electrocatalysts with low cost and high catalytic activity. Herein, N-doped carbon spheres (N-CS) with rich micropore structure have been synthesized by a facile two-step method, which includes the polymerization of pyrrole and formaldehyde and followed by a facile pyrolysis process. During the preparation, zinc chloride (ZnCl2) was utilized as a catalyst to promote polymerization and provide a hypersaline environment. In addition, the morphology, defect content and activity area of the resultant N-CS catalysts could be regulated by controlling the content of ZnCl2. The optimum N-CS-1 catalyst demonstrated much better catalytic activity and durability towards ORR in alkaline conditions than commercial 20 wt% Pt/C catalysts, of which the half-wave potential reached 0.844 V vs. RHE. When applied in the Zn-air batteries as cathode catalysts, N-CS-1 showed a maximum power density of 175 mW cm-2 and long-term discharging stability of over 150 h at 10 mA cm-2, which outperformed 20 wt% Pt/C. The excellent performance could be due to its ultrahigh specific surface area of 1757 m2 g-1 and rich micropore channels structure. Meanwhile, this work provides an efficient method to synthesize an ultrahigh surface porous carbon material, especially for catalyst application.

Activated red mud (RM) has been proved to be a promising base material for the selective catalysis reduction (SCR) of NOx. The inherent low reducibility and acidity limited its low–temperature activity. In this work, molybdenum oxide, tungsten oxide, and cerium oxide were used to reconfigure the redox sites and acid sites of red mud based catalyst. When activated red mud was reconfigured by cerium-tungsten oxide (Ce–W@RM), the NOx conversion kept above 90% at 219–480 °C. The existence of Ce3+/Ce4+ redox electron pairs provided more surface adsorbed oxygen (Oα) and served as a redox cycle. Positive interactions between Ce, W species and Fe oxide in red mud occurred, which led to the formation of unsaturated chemical bond and promoted the activation of adsorbed NH3 species. WO3 and Ce2(WO4)3 (formed by solid–state reaction between Ce and W species) could provide more Bronsted acid sites (W–O modes of WO3, W O or W–O–W modes of Ce2(WO4)3). CeO2 species could provide more Lewis acid sites. The Langmuir–Hinshelwood (L-H) routes and Eley-Rideal (E-R) routes occurred in the low-temperature SCR reaction on the Ce–W@RM surface. NH4+ species on Bronsted acid sites, NH3 species on Lewis acid sites, bidentate nitrate and bridging nitrate species were key active intermediates species.

A novel strategy was developed to fabricate FeNx-doped carbon quantum dots (Fe-N-CQDs) to detect Cu2+ ions selectively as a fluorescence probe. The Fe-N-CQDs were synthesized by an efficient electrolysis of a carbon cloth electrode, which was coated with monoatomic iron-anchored nitrogen-doped carbon (Fe-N-C). The obtained Fe-N-CQDs emitted blue fluorescence and possessed a quantum yield (QY) of 7.5%. An extremely wide linear relationship between the Cu2+ concentration and the fluorescence intensity was obtained in the range from 100 nM to 1000 nM (R2 = 0.997), and the detection limit was calculated as 59 nM. Moreover, the Fe-N-CQDs demonstrated wide range pH compatibility between 2 and 13 due to the coordination between pyridine nitrogen and Fe3+, which dramatically reduced the affection of the protonation and deprotonation process between H+ and Fe-N-CQDs. It is notable that the Fe-N-CQDs exhibited a rapid response in Cu2+ detection, where stable quenching can be completed in 7 s. The mechanism of excellent selective detection of Cu2+ was revealed by energy level simulation that the LUMO level of Fe-N-CQDs (−4.37 eV) was close to the redox potential of Cu2+, thus facilitating the electron transport from Fe-N-CQDs to Cu2+.

Biodegradable magnesium (Mg) and its alloy show huge potential as temporary bone substitute due to the favorable biocompatibility and mechanical compatibility. However, one issue deserves attention is the too fast degradation. In this work, mesoporous bioglass (MBG) with high pore volume (0.59 cc/g) and huge specific surface area (110.78 m2/g) was synthesized using improved sol-gel method, and introduced into Mg-based composite via laser additive manufacturing. Immersion tests showed that the incorporated MBG served as powerful adsorption sites, which promoted the in-situ deposition of apatite by successively adsorbing Ca2+ and HPO42−. Such dense apatite film acted as an efficient protection layer and enhanced the corrosion resistance of Mg matrix, which was proved by the electrochemical impedance spectroscopy measurements. Thereby, Mg based composite showed a significantly decreased degradation rate of 0.31 mm/year. Furthermore, MBG also improved the mechanical properties as well as cell behavior. This work highlighted the advantages of MBG in the fabrication of Mg-based implant with enhanced overall performance for orthopedic application.

Establishing highly effective charge transfer channels in carbon nitride (g-C3N4) to enhance its photocatalytic activity is still a challenging issue. Herein, the delaminated 2D Ti3C2 MXene nanosheets were employed to decorate the P-doped tubular g-C3N4 (PTCN) for engineering 1D/2D Schottky heterojunction (PTCN/TC) through electrostatic self-assembly. The optimized PTCN/TC exhibited the highest hydrogen evolution rate (565 μmol/h/g), which was 4.3 and 2.0 -fold higher than pristine bulk g-C3N4 and PTCN, respectively. Such enhancement may be primarily attributed to the phosphorus heteroatom doped and unique structure of 1D/2D g-C3N4/Ti3C2 Schottky heterojunction, enhancing the light-harvesting and charges’ separation. One-dimensional pathway of g-C3N4 tube and built-in electric field of interfacial Schottky effect can significantly facilitate the spatial separation of photogenerated charge carriers, simultaneously inhibit their recombination via Schottky barrier. In this composite, metallic Ti3C2 was served as electrons sink and photons collector. Moreover, ultrathin Ti3C2 flake with exposed terminal metal sites as a co-catalyst exhibited higher photocatalytic reactivity in H2 evolution compared to carbon materials (such as reduced graphene oxide). This work not only proposed the mechanism of tubular g-C3N4/Ti3C2 Schottky junction in photocatalysis, but also provided a feasible way to load ultrathin Ti3C2 as a co-catalyst for designing highly efficient photocatalysts.

Diphenyl carbonate (DPC) is one of the versatile carbonates, and is often used for the production of polycarbonates. In recent years, the catalytic synthesis of DPC has become an important topic but the development of a highly active metal-free catalyst is a great challenge. Herein, a series of ionic liquids-SBA-15 hybrid catalysts with different functional groups have been developed for the synthesis of DPC under solvent-free condition, which are effective and clean instead of the metal-containing catalysts. It is found that in the presence of [SBA-15-IL-OH]Br catalyst, methyl phenyl carbonate (MPC) conversion of 80.5% along with 99.6% DPC selectivity is achieved, the TOF value is thrice higher than the best value reported by using transition metal-based catalysts. Moreover, the catalyst displays remarkable stability and recyclability. This work provides a new idea to design and prepare eco-friendly catalysts in a broad range of applications for the green synthesis of carbonates.

Hydrogen energy has long been recognized as a clean alternative to conventional fossil fuels, which can be applied in a wide range of transportation and power generation applications. The rational design and engineering of high-performance and robust catalysts for hydrogen evolution reaction (HER) shows not a great significance but a challenge for efficient electrochemical water splitting. Herein, a new type of Ni-based Ni-ABDC precursor has been obtained, which leads to the formation of N-doped porous carbon nanomaterials uniformly coated with well-proportioned bimetallic AgNi alloys via a stepwise strategy. To their credit, all samples of AgNi/NC-X are structurally calcined from the pristine AgNi-ABDC-X by tuning the different concentration of AgNO3, which means all of them maintain the vermicelli-like morphology compared with Ni-ABDC. The series of AgNi/NC-X materials can be regarded as effective electrocatalysts for HER both in acidic and alkaline media, but an acid-leaching phenomenon is observed. Among them, the as-prepared AgNi/NC-2 exhibits a low overpotential of 103 mV at the current density of 10 mA cm−2 and decent durability with a high retention rate of 90.9% after 10 h in 1.0 M KOH electrolyte. The compelling HER properties of AgNi/NC-2 can be attributed to the synergistic effect between the hierarchical carbon materials, partial N-doping and abundant AgNi alloys. Meanwhile, this study provides a practicable method for the development of efficient HER electrocatalysts for energy applications, which can be conveniently prepared through the reasonable introduction of active components in the crystalline inorganic-organic precursors.

Along with the environmental pollution, the scarcity of clean water seriously threatens the sustainable development of human society. Recently, the rapid development of solar evaporators has injected new vitality into the field of water purification. However, the industry faces a considerable challenge of achieving comprehensive purification of ions, especially the efficient removal of mercury ions. In this work, we introduce an ideal mercury-removal platform based on facilely and cost-effectively synthesized polysulfide nanoparticles (PSNs). Further development of PSN-functionalized reduced graphene oxide (PSN-rGO) aerogel evaporator results in achieving a high evaporation rate of 1.55 kg m−2 h−1 with energy efficiency of 90.8% under 1 sun. With the merits of interconnected porous structure and adsorption ability, the photothermal aerogel presents overall purification of heavy metal ions from wastewater. During solar desalination, salt ions can be rejected with long-term stability. Compared with traditional water purification technologies, this highly efficient solar evaporator provides a new practical method to utilize clean energy for clean water production.

Adsorptive removal of heavy metal ions from wastewater is very important, and the key is the development of efficient sorbents. In this work, oxygenated alkynyl carbon materials (OACMs) were synthesized via mechanochemical reaction of CaC2 and a carbonate (CaCO3, Na2CO3, or NaHCO3) at ambient temperature. The resultant OACMs are micro mesoporous carbon nanomaterials with high specific area (>648 m2 g−1), highly crosslinked texture, and rich alkynyl and oxygenated groups. The OACMs exhibit excellent Hg(II) adsorption due to the soft acid-soft base interaction between alkynyl and Hg(II), and OACM-3 derived from CaC2 and NaHCO3 has the saturated Hg(II) adsorbance of 483.9 mg g−1 along with good selectivity and recyclability. The adsorption is mainly chemisorption following the Langmuir mode. OACM-3 also shows high adsorbance for other heavy metal ions, e.g. 256.6 mg g−1 for Pb(II), 232.4 mg g−1 for Zn(II), and 198.7 mg g−1 for Cu(II). This work expands the mechnochemical reaction of CaC2 with carbonates and possibly other oxyanionic salts, provides a new synthesis approach for functional alkynyl carbon materials with excellent adsorption performance for heavy metal ions, as well as a feasible approach for CO2 resource utilization.

Aqueous zinc-air battery (ZAB) has attractive features as the potential energy storage system such as high safety, low cost and good environmental compatibility. However, the issue of dendrite growth on zinc metal anodes has seriously hindered the development of ZAB. Herein, the N-doped carbon cloth (NC) prepared via magnetron sputtering is explored as the substrate to induce the uniform nucleation of zinc metal and suppress dendrite growth. Results show that the introduction of heteroatoms accelerates the migration and deposition kinetics of Zn2+ by boosting the desolvation process of Zn2+, eventually reducing the nucleation overpotential. Besides, theoretical calculation results confirm the zincophilicity of N-containing functional group (such as pyridine N and pyrrole N), which can guide the nucleation and growth of zinc uniformly on the electrode surface by both promoting the redistribution of Zn2+ in the vicinity of the surface and enhancing its interaction with zinc atoms. As a result, the half-cell assembled with magnetron sputtered carbon cloth achieves a high zinc stripping/plating coulombic efficiency of 98.8% and long-term stability of over 500 cycles at 0.2 mA cm-2. And the Coulombic efficiency reached about 99.5% at the 10th cycle and maintained for more than 210 cycles at a high current density of 5.0 mA cm-2. The assembled symmetrical battery can deliver 220 plating/stripping cycles with ultra-low voltage hysteresis of only 11 mV. In addition, the assembled zinc-air full battery with NC-Zn anode delivers a high special capacity of about 429 mAh gZn-1 and a long life of over 430 cycles. The effectiveness of surface functionalization in promoting the transfer and deposition kinetics of Zn2+ presented in this work shows enlightening significance in the development of metal anodes in aqueous electrolytes.

Covalent organic frameworks (COFs) are nanoporous crystalline polymers with densely conjugated structures. This work discovers that imine-linked COFs exhibit remarkable photodegradation efficiency to azo dyes dissolved in water. Visible light generates different types of radicals from COFs, and superoxide radicals break N N bonds in dye molecules, resulting in 100% degradation of azo dyes within 1 h. In contrast, these dyes cannot be degraded by conventionally used photocatalysts, for example, TiO2. Importantly, the COF photocatalysts can be recovered from the dye solutions and re-used to degrade azo dyes for multiple times without loss of degradation efficiency. This work provides an efficient strategy to degrade synthetic dyes, and we expect that COFs with designable structures may use as new photocatalysts for other important applications.

Graphene oxide (GO) is regarded as a promising candidate to construct solar absorbers for addressing freshwater crisis, but the easy delamination of GO in water poses a critical challenge for practical solar desalination. Herein, we improve the stability of GO membranes by a self-crosslinking poly (ionic liquid) (PIL) in a mild condition, which crosslinks neighbouring GO nanosheets without blemishing the hydrophilic structure of GO. By further adding carbon nanotubes (CNTs), the sandwiched GO/CNT@PIL (GCP) membrane displays a good stability in pH = 1 or 13 solution even for 270 days. The molecular dynamics simulation results indicate that the generation of water nanofluidics in nanochannels of GO nanosheets remarkably reduces the water evaporation enthalpy in GCP membrane, compared to bulk water. Consequently, the GCP membrane exhibits a high evaporation rate (1.87 kg m−2 h−1) and displays stable evaporation rates for 14 h under 1 kW m−2 irradiation. The GCP membrane additionally works very well when using different water sources (e.g., dye-polluted water) or even strong acidic solution (pH = 1) or basic solution (pH = 13). More importantly, through bundling pluralities of GCP membrane, an efficient solar desalination device is developed to produce drinkable water from seawater. The average daily drinkable water amount in sunny day is 10.1 kg m−2, which meets with the daily drinkable water needs of five adults. The high evaporation rate, long-time durability and good scalability make the GCP membrane an outstanding candidate for practical solar seawater desalination.

This study aimed to control lesser grain borer Rhizopertha dominica via using of Zingier officinale (ginger) and Helianthus annuus (sunflower) oils as protectant of Tritium spp. The inhibition rates were 38.00, 28.98, 22.67 and 4.60% respectively when the wheat treated by 0.5, 1, 1.5and 2% of sunflower oil while the inhibition rates were 35.50, 28.00, 7.25 and 3.25% respectively when the wheat treated by the same concentrations of Z. officinale oil. The damage assessments were decreased while increasing the concentration of the oils, the H. annuus oil is more protectant than Z . officinale oil in 2%. Approximately the two plant oils caused same damage percentage when the wheat treated by 1% during storage. To sum up, the results strengthen the possibility of using the plant oils for the management this insect. http://dx.doi.org/10.25130/tjps.23.2018.026

Glyceryl monolaurate (GML), as one of widely used industrial chemicals, can be synthesized via Fischer esterification of lauric acid (LA) and glycerol (GL). In this work, we screened boric acid-based deep eutectic solvent (DES) formed from tetrapropylammonium bromide (TPAB) and boric acid to intensify the selective Fischer esterification through conductor-like screening model for realistic solvents (COSMO-RS) theory. The solid liquid equilibrium (SLE) phase behavior, hydrogen bond formation process, and thermal stability of the DES were characterized by differential scanning calorimetry (DSC), Fourier transform infrared spectrometry (FT-IR), and thermogravimetric analyzer (TGA). The results verified that equimolar TPAB and boric acid formed DES [TPAB:B(OH)3] with the lowest freezing point and very good thermal stability could efficiently intensify the Fischer esterification of GL and LA to GML. The hydrogen bond accepter TPAB of the DES made the esterification system homogeneous, which promoted the selective esterification process. In addition, the hydrogen bond donor B(OH)3 of the [TPAB:B(OH)3] combined with diol unit of GL to cyclic boric esters and led to a special selective space effect, which also improved the selectivity to GML. Thus, the esterification intensified of GL and LA by 20 wt% DES achieved GML selectivity of 85.7 % and yield of 76.4 % under the optimal reaction conditions. The esterification kinetics suggested the reaction followed pseudo-second-order model and the reaction activation energy was 33.98 kJ mol−1, similar to and/or lower than those reported works. Furthermore, DES and unreacted glycerol were readily recovered and reused through temperature controlled gravity-based separation due to the ability of homogeneity under reaction conditions and splitting phase behavior during the DES recovery. The results can expand the boric acid-based DESs for other potential intensification applications.

Poly methyl methacrylate (PMMA) is one of the most widely used materials in modern prosthodontics. It is widely known due to its simplicity in use and acceptable aesthetic. A new concept of polymerization fluid resin technique was instead of heat and gypsum material. Forty specimens were prepared from two brands of fluid acrylic resin. The samples were divided into two groups, the first one was the control while the other group was incorporated with silver nanoparticles(modified). The tests performed were impact strength, transverse strength, color stability and candida retention ability on the samples. 10 samples for each test were used. The results showed that modified group had significantly higher impact strength than the control group. There was non-significant difference between group of modified fluid acrylic and control group. Regarding color stability, there were highly significant color change after 10 days of immersion in the tea solution for the modified group the results of the biological test showed that the candida retention of the control group was significantly higher than modified group. Within the limitation of this study it can be concluded that addition of silver nanoparticles has resulted in significant difference between control and modified group for impact strength test. While non-significant difference was seen for transverse strength test. In regard to color stability, showed enhancement in color stability for both before and after placement in tea solution. Addition of silver nanoparticles also caused reduction in candida albicans retention in the added samples.

The uniaxial ratchetting-fatigue interaction of extruded AZ31 magnesium (Mg) alloy is investigated by uniaxial stress-controlled cyclic tests at room temperature and with addressing the roles of different plastic deformation mechanisms. Different stress levels are prescribed to reflect the cyclic plasticity of the alloy controlled by diverse deformation mechanisms (i.e., dislocation slipping, deformation twinning and detwinning ones), and then the influences of stress level and stress rate on the ratchetting and fatigue life are discussed. The experimental results demonstrate that different evolution characteristics of whole-life ratchetting and fatigue life presented during cyclic tests with various mean stresses, stress amplitudes and stress rates are determined by the dominated plastic deformation mechanisms. It's worth noting that the ratchetting can occur in the compressive direction even in the cyclic tests with a positive (tensile) mean stress, and the fatigue life increases first and then decreases with the increase of mean stress on account of the interaction between dislocation slipping and twinning/detwinning mechanisms. Comparing the fatigue lives obtained in the asymmetric stress-controlled and symmetrical strain-controlled cycle tests, it is seen that the ratchetting deformation causes an additional damage, and then leads to a shortening of fatigue life.

To clarify the anodic dissolution mechanism of Mg, the hydrogen evolution from pure Mg in acidic solutions under galvanostatic conditions were systematically measured. With increasing anodic current density, the cathodic hydrogen evolution rate decreased, and the anodic hydrogen evolution became faster while some surface area on the Mg was becoming dark under anodic polarization. Based on the surface analysis results and the generally accepted basic electrochemical equations, the evolution kinetics of hydrogen from Mg was deduced, and the most possible surface intermediate active species that could facilitate the anodic Mg dissolution and anodic hydrogen evolution were proposed. This paper further develops the model of incomplete film Mg+ dissolution, explains many reported experimental phenomena, and clarifies misunderstandings of current mechanism.

Additive manufacturing (AM) of Mg alloys has become a promising strategy for producing complex structures, but the corrosion performance of AM Mg components remains unexploited. In this study, wire and arc additive manufacturing (WAAM) was employed to produce single AZ31 layer. The results revealed that the WAAM AZ31 was characterized by significant grain refinement with non-textured crystallographic orientation, similar phase composition and stabilized corrosion performance comparing to the cast AZ31. These varied corrosion behaviors were principally ascribed to the size of grain, where cast AZ31 and WAAM AZ31 were featured by micro galvanic corrosion and intergranular corrosion, respectively.

A composite system consisting of aminosilicate (APS) functionalized-fullerene quantum dots (C60 QDs) and bismuth vanadate (BiVO4-APS-C60) has been developed via a facile one-step hydrothermal process. The structural analysis by XRD revealed that the integrated QDs have not affected the crystal structure of the host BiVO4, while the XPS studies showed that these QDs have been integrated via the Bi-V-O-Si-C network. The optical studies indicated that both the C60 and APS-C60 QDs have hardly influenced the optical absorption properties of the composite system. On the other hand, the dispersion of aminosilicate functionalized-QDs considerably reduced the aggregation in the layers and yielded a few nanometer thick BiVO4 layers due to their inter-layer occupancy as seen from their high-resolution TEM images. The photoluminescence, photocurrent and electrochemical impedance studies showed that the integration of APS-C60 QDs greatly improved the photoactive properties of the composite by effectively enhancing the charge recombination resistance, charge separation and transfer process between the integrated materials and surroundings. As a result, BiVO4-APS-C60 composites showed the enhanced photocatalytic efficiency towards degradation of ciprofloxacin (CIP) molecules under solar light irradiation as compared to that of bare-BiVO4 and BiVO4-C60.

The idea of the Internet of Things that everything is linked to anything and everything interacts with the other is a great idea, and that the topic of integrating these devices will add a remarkable change in this world and increase its prosperity, and this interconnection occurs through the exchange of data and information and facilitating our communication with the things around us. But questions about security and privacy remain. When this massive amount of data is exchanged, it will certainly be an attractive environment for attackers and hackers. In this paper, we will present the issues of security and privacy, their main requirements, potential risks and tools to defend these risks, and a detailed review of security attacks in order to be able to deter these attacks achieve confidentiality, security and reliability for users.

Microstructural evolution and strengthening mechanisms of Mg-3Sn-1Ca based alloys with additions of different amounts of AlN nano-particles were investigated. It was found that with increasing the amount of AlN nano-particles the grain size decreases obviously. The existence of AlN nano-particles could refine the primary crystal phases CaMgSn, which provided more heterogeneous nucleation sites for the formation of magnesium. Moreover, such nano-particles could also restrict the grain growth during solidification. After adding AlN nano-particles, both the tensile properties at room temperature and high temperature 250 °C and the hardness are largely improved. The improvement of strength is attributed to grain refinement and second phase refinement.

Solar cell layers technology has achieved global standing in the solar cell layers deposition process, and it covers the innovative methods and techniques in significant applications. Recent solar cell layers technology has an advanced interest in a refined approach to enhance performance and highlights the importance of recent proficient procedures for manufacturing. For example, the application is used to search for novel materials for solar cells' layers to clarify the current energy crisis. The technological process and various types of solar cells depend on climate change. Among them, layers of solar cells and silicon wafer solar cells are very encouraging. Solar cell layers technology has led to solar cells being a more reasonable active option in design and production. The productivities facilitated by new solar cells still need to be enhanced for the various processes involved in the additional enhancement from Copper Indium Gallium Selenide (CIGS) microfilms to solar cell crystal structure dye-sensitized solar cells. The hydrophobic coating works as an anti-dust coating, enhancing efficiency and decreasing the cost of cleaning solar cells. In Saudi Arabia Majmaah City, most solar projects are in dry regions, where the dusty weather reduces solar cell efficiency. Therefore, combining these two properties and applying an anti-reflective and superhydrophobic coating will increase solar cell efficiency by 20%. Solar cells' crystal structure results are substituted with layers or new materials to balance environmental impact and toxic nature.

High surface area cerium oxide was synthesized via the reverse microemulsion method and assessed for CO2 reduction to CO via reverse water gas shift. The resulted ceria nanoparticles (ca. 4 nm) were 100% selective to CO formation, while attaining a nearly equilibrium CO2 conversion at 600 °C. As compared to ceria synthesized by wet precipitation, the reverse microemulsion-synthesized ceria exhibited enhanced surface stability and a more stable catalytic performance (declining from 63% to 50% over 100 h on stream). No significant carbon formation was detected and a relatively small decline in conversion was related to the specific surface area reduction induced by the growth of ceria nanoparticles under the reaction conditions.

The heterogeneous magnesium (Mg) matrix nanocomposite with dispersed soft phase exhibits high strength and toughness. Herein, the deformation behavior and failure process were investigated to reveal the unique mechanical behavior of the heterogeneous microstructure under compression. The extensive plastic deformation is accompanied by the flattening and tilting of the soft phase, inhibiting strain localization and leading to strain hardening. Moreover, a stable crack multiplication process is activated, which endows high damage tolerance to the heterogeneous Mg matrix nanocomposites. The final failure of the composite is caused by crack coalescence in the shear plane along a tortuous path. The presence of dispersed soft phases within the hard matrix induces a noticeable change in mechanical response. Especially, the malleability of the heterogeneous Mg matrix nanocomposite is two and ten times higher than that of pure Mg and the homogeneous Mg matrix nanocomposite, respectively. The current study provides a novel strategy to break the trade-off between strength and toughness in metal matrix nanocomposites.

Pulmonary fibrosis (PF) is an irreversible lung disease that is characterized by excessive scar tissue with a poor median survival rate of 2–3 years. The inhibition of TGF-β receptor type-I (TGF-β RI) by an appropriate drug may provide a promising strategy for the treatment of this disease. Polygonum cuspidatum (PC) is a well-known traditional Chinese herbal medicine which has an anti-PF effect. Accordingly, a combination of high resolution mass spectrometry and an in silico strategy was developed as a new method to search for potential chemical ingredients of PC that target the TGF-β RI. Based on this strategy, a total of 24 ingredients were identified. Then, absorption, distribution, metabolism, and excretion (ADME)-related properties were subsequently predicted to exclude compounds with potentially undesirable pharmacokinetics behaviour. Molecular docking studies for TGF-β RI were adopted to discover new PF inhibitors. Eventually, a compound that exists in PC known as resveratrol was proven to have excellent biological activity on TGF-β RI, with an IC50 of 2.211 μM in vitro. Furthermore, the complex formed through molecular docking was tested via molecular dynamics simulations, which revealed that resveratrol had strong interactions with residues of TGF-β RI. This study revealed that resveratrol has significant potential as a treatment for PF due to its ability to target TGF-β RI. In addition, this research demonstrated the exploration of natural products with excellent biological activities toward specific targets via high resolution mass spectrometry in combination with in silico technology is a promising strategy for the discovery of novel drugs.

Novel dual-ionic imidazolium salts are shown to display excellent catalytic activity for cycloaddition of carbon dioxide and epoxides under room temperature and atmospheric pressure (0.1 MPa) without any solvent and co-catalyst leading to 96.1% product yield. It can be reused five times to keep the product yield over 90%. These intriguing results are attributed to a new reaction mechanism, which is supported by theoretical calculations along with the measurements of 13C NMR spectrum and Fourier transform infrared spectroscopy (FT-IR). The excellent catalytic activity can be traced to a CO2-philic group along with an electrophilic hydrogen atom. Our work shows that incorporation of CO2-philic group is an feasible pathway to develop the new efficient ionic liquids.

Based on the deforming technique of severe plastic deformation (SPD), the grain refinement of a Mg-9Gd-3Y-2Zn-0.5Zr alloy treated with decreasing temperature reciprocating upsetting-extrusion (RUE) and its influence on the mechanical properties and wear behavior of the alloy were studied. The RUE process was carried out for 4 passes in total, starting at 0 °C and decreasing by 10 °C for each pass. The results showed that as the number of RUE passes increased, the grain refinement effect was obvious, and the second phase in the alloy was evenly distributed. Room temperature tensile properties of the alloy and the deepening of the RUE degree showed a positive correlation trend, which was due to the grain refinement, uniform distribution of the second phase and texture weakening. And the microhardness of the alloy showed that the microhardness of RUE is the largest in 2 passes. The change in microhardness was the result of dynamic competition between the softening effect of DRX and the work hardening effect. In addition, the wear resistance of the alloy showed a positive correlation with the degree of RUE under low load conditions. When the applied load was higher, the wear resistance of the alloy treated with RUE decreased compared to the initial state alloy. This phenomenon was mainly due to the presence of oxidative wear on the surface of the alloy, which could balance the positive contribution of severe plastic deformation to wear resistance to a certain extent.

Co-pyrolysis of lignin and waste plastics, for example polyethylene (PE), has been studied, but related reports are basically on condition optimizations. This study revealed a new perspective on PE-promoted lignin pyrolysis to phenolic monomers with mass transfer and radical explanation. Lignin and PE were first pyrolyzed individually to identify pyrolysis characteristics, pyrolytic products, as well as the suitable co-pyrolysis temperature. Then, co-pyrolysis of blended lignin/PE with various ratios was investigated. Yields of lignin products reached the maximum under lignin/PE ratio of 1:1, but blended approach always inhibited the production of lignin phenols. This resulted from the poor mass transfer and interactions between lignin and PE, in which PE pyrolysates could easily escape from the particle gaps. While in layered approach, PE pyrolysates had to pass through the lignin layer which contributed to the good interactions with lignin pyrolysis intermediates, thus the yields of lignin-derived products were significantly improved. Interactions between lignin and PE (or their pyrolysates) were mainly radical quenching reactions, and X-ray photoelectron spectrum (XPS) and electron paramagnetic resonance (EPR) of pyrolytic chars were conducted to verify these interactions controlled by mass transfer. The percentage of C C (sp2) and concentration of organic stable radicals in layered lignin/PE char were both the lowest compared with those in blended lignin/PE and lignin char, indicating the stabilization of lignin-derived radicals by PE pyrolysates. Moreover, the spin concentration of radicals in the char from layered char/PE was lower than that in lignin char, which further affirmed the quenching of radicals by PE in the layered co-pyrolysis mode.

In this work, a novel bamboo-like carbon nanotubes@Sn4P3@carbon (BLCNTs@Sn4P3@C) coaxial nanotubes are designed and prepared using a newly developed hydrothermal method followed by a phophidation process. The prepared Sn4P3 nanoparticles are uniformly coated and wrapped on the one-dimensional (1D) bamboo-like CNTs, which is covered by a uniform carbon layer to form a sandwich-like structure with Sn4P3 in between. The inner CNT and outer carbon can effectively maintain the structural stability and serve as the good electron conductors. Additionally, the outer carbon coating layer can effectively keep BLCNTs@Sn4P3@C nanotubes separate each other, preventing aggregation of Sn4P3 during charge/discharge when this material is used as anode for sodium ion batteries. The anode of BLCNTs@Sn4P3@C shows excellent reversible capacity and a long cycling of over 2000 cycles. The unique design of coaxial nanotubes is greatly beneficial to the electrochemical performance of Sn4P3 for sodium ion storage.

Side-chain alkylation of toluene with methanol is a green pathway to realize the one-step production of styrene under mild conditions, but the low selectivity of styrene is difficult to be improved with by-products of ethylbenzene and xylene. In this study, a new way is introduced to improve the catalytic performance by means of assisting basic compounds as co-catalysts during the toluene side-chain alkylation with methanol to styrene. As a result, high activity of side-chain alkylation appears over the basic Cs-modified zeolite catalysts prepared by ion exchange and impregnation methods. This high performance should be mainly attributed to two co-catalysis actions: (1) the promotion of basic compounds for methanol dehydrogenation to formaldehyde as the intermediate for side-chain alkylation; (2) the suppression of the styrene transfer hydrogenation on basic Cs-modified zeolites to avoid the formation of ethylbenzene. Especially for Cs2O/CsX-ex catalyst, the addition of 2 mol% 2-picoline in reaction mixture could achieve both 12.3% toluene conversion and 84.1% styrene selectivity. Whereas the higher concentration of 2-picoline (>6 mol%) caused an inhibition to the catalytic activity because the excessive basic compound poisoned the combined acid-base pathway required for the side-chain alkylation process. In addition, two possible side-chain alkylation reaction routes on Cs-modified zeolite under the different 2-picoline absorption were described.

Atomically dispersed precious metal catalysts maximize atom efficiency and exhibit unique reactivity. However, they are susceptible to sintering. Catalytic reactions occurring in reducing environments tend to result in atomically dispersed metals sintering at lower temperatures than in oxidative or inert atmospheres due to the formation of mobile metal-H or metal-CO complexes. Here, we develop a new approach to mitigate sintering of oxide supported atomically dispersed metals in a reducing atmosphere using organophosphonate self-assembled monolayers (SAMs). We demonstrate this for the case of atomically dispersed Rh on Al2O3 and TiO2 using a combination of CO probe molecule FTIR, temperature programmed desorption, and alkene hydrogenation rate measurements. Evidence suggests that SAM functionalization of the oxide provides physical diffusion barriers for the metal and weakens the interactions between the reducing gas and metal, thereby discouraging the adsorbate-promoted diffusion of metal atoms on oxide supports. Our results show that support functionalization by organic species can provide improved resistance to sintering of atomically dispersed metals with maintained catalytic reactivity.

In this work, we have prepared the hierarchically nanostructured core–shell NiCo layered double hydroxide (NiCo-LDH) nanosheets- and ZnFe2O4 nanocubes-decorated polyacrylonitrile (PAN)/pitch-based carbon nanofibers (PPCNs) webs (NiCo-LDH@PPCNs as cathode and ZnFe2O4@PPCNs as anode materials) with the bonded network structure by a facile and scalable hydrothemal method. Herein, the low-cost pitch with lower softening point (∼90 °C) as co-precursor was utilized to produce the PAN/pitch-based carbon nanofibers (PPCNs) with enhanced electrical conductivity. The obtained PPCNs with pitch content of 30% (PP30CNs) electrode material delivered higher specific capacitance (∼67 F g−1) than that (∼48 F g−1) of the PAN-based carbon nanofibers (PCNs) at 1 A g−1, due to the increased electrical conductivity and lower interfacial charge transfer resistance (RCT) of ∼0.16 Ω. Further, the NiCo-LDH-decorated PP30CNs (NiCo-LDH@PP30CNs) as cathode material showed superior specific capacitance of 1162 F g−1 at 1.0 A g−1 and ultra-high retention rate of 91.56% at 10 A g−1. The ZnFe2O4@PP30CNs as anode material also showed higher specific capacitance of 282 F g−1 at 1 A g−1 and good rate capability with capacitance retention of 56.73% at 10 A g−1. The as-fabricated asymmetric NiCo-LDH@PP30CNs//ZnFe2O4@PP30CNs hybrid supercapacitor device delivered a specific capacitance of ∼98 F g−1 at 1 A g−1 and excellent capacitance retention of ∼88% after 5000 charge–discharge cycles.