A simple approach for fabrication of interconnected graphitized macroporous carbon foam with uniform mesopore walls by using hydrothermal method

Three-dimensional (3D) highly interconnected graphitized macroporous carbon foam with uniform mesopore walls has been successfully fabricated by a simple and efficient hydrothermal approach using resorcinol and formaldehyde as carbon precursors. The commercially available cheap polyurethane (PU) foam and Pluronic F127 were used as a sacrificial polymer and mesoporous structure-directing templates, respectively. The graphitic structure of carbon foam was obtained by catalytic graphitization method using iron as catalyst. Three different carbon foams such as graphitized macro-mesoporous carbon (GMMC) foam, amorphous macro-mesoporous carbon (AMMC) foam and graphitized macroporous carbon (GMC) foam were fabricated and their physicochemical and mechanical properties were systematically measured and compared. It was found that GMMC possess well interconnected macroporous structure with uniform mesopores located in the macroporous skeletal walls of continuous framework. Besides, GMMC foam possesses a well-defined graphitic framework with high surface area (445 m²/g), high pore volume (0.35 cm³/g), uniform mesopores (3.87 nm), high open porosity (90%), low density (0.30 g/cm³) with good mechanical strength (1.25 MPa) and high electrical conductivity (11 S/cm) which makes it a promising material for many potential applications.     

Enhancing cation exchange capacity of chars through ozonation

The use of ozone to increase the cation exchange capacity (CEC) of two chars produced from pyrolysis of Douglas fir (Pseudotsuga menziessii) and a control bituminous coal activated carbon (AC) is reported. Chars were produced from the wood fraction of Douglas fir (DFWC) and the bark (DFBC) at 500 °C using an auger driven reactor with a nitrogen sweep gas under mild vacuum. Five ozone treatment times, ranging from 5 min to 60 min, were investigated. The initial properties of each char were found to differ significantly from the other samples in terms of surface area, proximate composition, and elemental composition. DFWC did not show significant mass loss or temperature variation during ozone treatment; however, after 1 h of oxidation both DFBC and AC samples resulted in 20% and 30% mass loss, respectively, and reactor temperatures in excess of 60 °C. Analysis of the pore size distribution of each treatment shows that ozone treatment did not significantly affect small micropores after 30 min of treatment for any material, but did reduce the apparent surface area of mesopores. Increases in carboxylic groups were identified with ozone treatment and found to correlate strongly with changes in measured CEC. The formation of lactone was found to correlate positively with reactor temperature during oxidation. These results indicate that the properties of chars, including surface area, pore structure, and chemical composition, as well as reactor conditions strongly affect the ozone oxidation of chars.     

Self-terminated electrodeposition of platinum on titanium nitride for methanol oxidation reaction in acidic electrolyte

The development of high-performance electrocatalysts for methanol oxidation is an urgent task to enhance the efficiency of direct methanol fuel cells. We report a simple and controllable method to fabricate Pt-decorated TiN electrocatalysts using self-terminated electrodeposition at room temperature and ambient pressure. Under optimized deposition parameters such as electrolyte pH, TiN substrate pretreatment, and pulsed deposition potential, quenching of the Pt electrodeposition facilitates obtaining an extremely low Pt mass loading (0.93 μg/cm²) on the TiN substrate. Repeated deposition potential pulses enable a gradual increase in Pt loading, with a precise control of the loaded Pt mass. Maximum intrinsic and mass activities for the methanol oxidation reaction are achieved for the catalyst with a Pt loading mass of 55.0 μg/cm², prepared by 20 deposition pulses. The maximum intrinsic activity achieved with the Pt-decorated TiN electrocatalyst is five times higher than that obtained with bulk Pt. The present results thus provide a facile method for the fabrication of cost-effective electrocatalysts.     

微波辅助合成3,4-二氨基苯甲酸

以对氨基苯甲酸为原料,在微波辐射下经乙酰化、硝化、水解及还原反应制得3,4-二氨基苯甲酸(Ⅰ),总收率为67．6%(未用微波辐射时为40．7%),反应时间由6 h缩短为1 h,并探讨了合成条件。在n(p- H2NC6H4COOH):n(Ac2O)=1:2,微波功率800 w的条件下,回流5 min,对乙酰胺基苯甲酸(Ⅱ)的收率为93．8%;n(Ⅱ):n(Ac2O)=1:2,使用过量乙酸酐,在冰水浴中滴完浓硝酸后,在微波功率800 W,回流3 min后,4-乙酰氨基-3-硝基苯甲酸(Ⅲ)的收率为85．3%;在微波功率800 W条件下,Ⅲ与过量的w(KOH)= 50%乙醇溶液,回流5 min,3-硝基-4-氨基苯甲酸(Ⅳ)的收率为93．1%;在Ⅳ的乙醇溶液中,在回流温度下滴加w[(NH4)2S]=9%硫化铵溶液,然后,在微波功率800 W条件下,回流5 min,可得90．8%的目标产物Ⅰ。用IR、1H NMR对化合物Ⅰ～Ⅳ进行了表征。     

Photocatalytic evolution of hydrogen over mesoporous TiO2 supported NiO photocatalyst prepared by single-step sol–gel process with surfactant template

Photocatalytic activity of mesoporous titania supported nickel oxide photocatalyst synthesized by single-step sol–gel (SSSG) process combined with surfactant-assisted template method was investigated for hydrogen evolution from an aqueous methanol solution, in comparison with one prepared by conventional incipient wetness impregnation (IWI) method. In single-step sol–gel process, nickel precursor was introduced into the titania sol prepared with the aid of a surfactant template behaving as pore-controlling agent to attain meso-scaled pore. The single-step sol–gel photocatalyst was experimentally found to enhance the photocatalytic evolution of hydrogen rather than the impregnated one. The optimum level of nickel loading in photocatalytic activity test for single-step sol–gel method was slightly higher than that for incipient wetness impregnation method. Characterization results demonstrated the significant modification of physical characteristics of the single-step sol–gel photocatalyst, anticipated to relating to the observation of higher photocatalytic hydrogen evolution activity.     

A Strategy of Liquid-Grafted Slippery Sponges with Simultaneously Enhanced Absorption and Desorption Performances for Crude Oil Spill Remediation

Crude oil spill accidents pose a worldwide environmental threat. Oleophilic and hydrophobic absorbents that can selectively absorb oil from water have shown promising application potential in oil spill remediation. Simultaneous optimization of the absorption and desorption speed of absorbents towards oil is highly desirable for their recyclable usage, but remains a great challenge, because these two properties are generally conflicting. Here, a facile and ingenious strategy is proposed to tackle the above challenge via surface modification of porous sponges with highly flexible linear polydimethylsiloxane (LPDMS) brushes. The LPDMS brushes feature liquid-like properties at room temperature owing to its extremely low glass transition temperature, and act as a covalently-grafted lubrication layer throughout the 3D network channels of the sponge, which can minimize contact angle hysteresis and reduce friction between oil and sponge channel. Compared to the prevalent cross-linked polydimethylsiloxane (CPDMS) modification strategy, sponges modified with LPDMS brushes not only shows significantly enhanced absorption speed, but also exhibits superior desorption dynamics towards viscous crude oils. The design strategy of slippery sponges with liquid-like molecules may open a new avenue for developing advanced absorbents with simultaneously enhanced absorption and desorption performances for liquid separation and purification applications.     

LiNO3-NaNO3-KNO3三元熔盐材料的设计及热稳定性研究

采用共形离子溶液模型(conformalionic solution model, CIS) 在二元熔盐体系相图的基础上，对三元熔盐体系LiNO₃-NaNO₃-KNO₃进行了相图计算，得到该三元体系最低共熔点为117.7℃，相应的摩尔分数组成分别为x(LiNO₃) = 0.375，x(NaNO₃) = 0.075，x(KNO₃) = 0.550。按照热力学最低共熔点计算结果，采用熔融法制备了三元硝酸熔盐，通过DSC和TG实验测定其最低共熔点为118.3℃，这与计算得到的结果(117.7℃)基本一致。TG测试结果表明当温度低于587.2℃时，该三元熔盐体系较为稳定，其工作温度范围为118.3~587.2℃，该三元硝酸熔盐适合在太阳能热发电中作为高温传热蓄热材料使用。     

Phi zeolite synthesized by template-free method for selective catalytic reduction of NO

Nitrogen oxide (NO_x) is one of the major air pollutants. Using a copper-based zeolite with a chabazite structure (CHA) as a catalyst, the selective catalytic reduction (SCR) technology can effectively remove NO_x. This work introduces a low silica CHA type zeolite with structural defects (zeolite Phi, with Si/Al of 4.7). The zeolite Phi is synthesized through a hydrothermal method without adding any template, which is low-cost and environment-friendly. The Cu-exchanged Phi is abundant of surface acidity and isolated Cu²⁺, showing a superior low-temperature activity, a wide work temperature window and a good hydrothermal stability. The presence of Na or Mg decreases the surface acidity and isolated Cu²⁺. The hydrothermally aged Na,Cu/Phi and Mg,Cu/Phi present different levels of framework collapse, which correspondingly induces catalyst deactivation.     

Biomolecules-Incorporated Metal-Organic Frameworks Gated Light-Sensitive Organic Photoelectrochemical Transistor for Biodetection

Incorporating biomolecules into metal-organic frameworks (MOFs) as exoskeletons to form biomolecules-MOFs biohybrids has attracted great attention as an emerging class of advanced materials. Organic devices have been shown as powerful platforms for next-generation bioelectronics, such as wearable biosensors, tissue engineering constructs, and neural interfaces. Herein, biomolecules-incorporated MOFs as innovative gating module is realized for the first time, which is exemplified by biocatalytic precipitation (BCP)-oriented horseradish peroxidase (HRP)-embedded zeolitic imidazolate framework-90 (HRP@ZIF-90)/CdIn₂S₄ gated organic photoelectrochemical transistor under light illumination. In connection to a sandwich immunocomplexing targeting the model analyte human IgG, the IgG-dependent generation of H₂O₂ and the tandem HRP-triggered BCP reaction can cause the in situ blocking of the pore network of ZIF-90, leading to variant gating effect with corresponding responses of the device. This representative biodetection achieved good analytical performance with a wide linear range and a low detection limit of 100 fg mL⁻¹. In the view of the plentiful biomolecule-MOF complexes and their potential interactions with organic systems, this study provides a proof-of-concept study for the generic development of biomolecules-MOFs-gated electronics and beyond.     

Optimizing the Oxygen-Catalytic Performance of Zn–Mn–Co Spinel by Regulating the Bond Competition at Octahedral Sites

By using the more electro-negative Mn³⁺ ion to partially replace Co³⁺ at the octahedral site of spinel ZnCo₂O₄, i.e., forming ternary Zn–Mn–Co spinel oxide, the electrocatalytic oxygen reduction/evolution activity is found to be significantly increased. Considering the physical characterization and theoretical calculations, it demonstrated that the bond competition played a key role in regulating the cobalt valence state and the electrocatalytic activity. The partial replacement of octahedral-site-occupied Co³⁺ by Mn³⁺ can effectively modulate the adjacent Co–O bond and induce the Jahn–Teller effect, thus changing the originally stable crystal structure and optimizing the binding strength between the active center and reaction intermediates. Certainly, the Mn-substituted ZnMn_1.4Co_0.6O₄/NCNTs exhibit higher electrocatalytic oxygen reduction reaction (ORR) activity than that of ZnCo₂O₄/NCNTs and ZnMn₂O₄/NCNTs, supporting that the Co–O bond covalency determines the ORR activity of spinel ZnCo₂O₄. This study offers the competition between adjacent Co–O and Mn–O bonds via the B_Oh–O–B_Oh edge-sharing geometry. The ion substitution at octahedral sites by less electronegative cations can be a new and effective way to improve the electrocatalytic performance of cobalt-based spinel oxides.