细菌纤维素/碳纳米管/MnO2复合超级电容器电极

基于细菌纤维素(BC)的三维多孔及柔性支架结构和碳纳米管(MWCNT)的优良导电性,构筑起BC/MWCNT自支撑导电基底。其中,二者通过氢键紧密结合,协同赋予复合基底优良的电导率和机械性能。然后将二氧化锰(MnO₂)电沉积在该基底上,构建了一种新型的BC/MWCNT/MnO₂薄膜电极。BC/MWCNT复合膜的多孔结构、电解质吸收特性及蜂窝状活性MnO₂纳米片的桥连结构,赋予其出色的电化学性能(在1 mA cm_-2^{的电流密度下},其面积比电容和质量比电容分别达到1.17 F cm_-2^和200 F g_-1⁾和显著的循环稳定性(在20 mA cm_-2^{的电流密度下进行}10000次循环后,其比电容保留率稳定在96%)。这种无粘合剂的薄膜电极制备简便且成本低廉,在开发柔性储能器件方面具有巨大潜力。关键词：细菌纤维素(BC)；碳纳米管(MWCNT)；二氧化锰(MnO₂)；膜电极；电化学性能中图分类号：TQ630 文献标识码： A 文章编号：1003-5214 (2020) 01-0000-00     

木焦油基活性碳的制备及其对亚甲基蓝的吸附性能研究

木焦油是木质生物质材料的高温裂解产物。以木焦油为碳源,以甲醛化处理后的木焦油为前体,通过碳化-活化制备木焦油基活性碳材料。并以制备的木焦油基活性碳为吸附剂,研究了其对模拟水体中亚甲基蓝的吸附性能。结果表明,以木焦油为前驱体经高温碳化活化制备的多孔活性碳,比表面积可达1373Sm_²?g_^-1,表面含有丰富的含氧官能团。木焦油基活性碳对亚甲基蓝具有良好的吸附性能,准二级动力学模型能更准确的描述木焦油基活性碳吸附亚甲基蓝的动力学过程。吸附等温线更符合Langmuir等温吸附模型,木焦油基活性碳对亚甲基蓝的最大吸附容量可达559 mg?g_^-1。热力学分析表明亚甲基蓝在木焦油基活性碳上的吸附是放热和自发的。利用木焦油制备的活性碳材料对亚甲基蓝具有较高的吸附容量,是一种具有潜在应用前景的吸附材料。     

环氧烷烃与硫代内酯交替共聚制备聚酯硫醚及性能探究

采用金属铬配合物/双-(三苯基正膦基)氯化铵/叔丁醇锂组成的三组分催化体系,实现了多种环氧烷烃与γ-硫代丁内酯(TBL)高活性开环共聚。发现聚合过程中叔丁醇锂可以有效稳定链末端硫负离子,抑制其回咬,保证了反应的活性以及聚合物的分子量。采用₁^H NMR、₁₃^C NMR、ESI-MS以及FTIR对聚合物结构进行了表征,通过DSC和TGA考察了不同结构聚酯硫醚的热性能。结果表明,聚酯硫醚均具有完全交替结构且呈现无定形态,玻璃化转变温度(T_g)处于?53~?18 °C之间,5%热失重温度在258~300 °C之间。通过氧化反应进一步获得含亚砜和砜结构单元的含硫聚合物,使得T_g大大提高。以叔丁基缩水甘油醚与TBL的共聚物为例,其硫醚结构被氧化为亚砜和砜结构后聚合物T_g分别提高了49和60 °C。     

The new organometallic rhodium–iron homogeneous catalytic system for hydroformylation

The addition of Fe(CO)₅ to the systems with [Rh(acac)(CO)L] complexes (L = PPh₃, P(OPh)₃, P(NC₄H₄)₃) as catalyst precursors caused the increase of aldehydes yield in 1-hexene hydroformylation reaction (80°C, 10 atm) up to 71%. The IR and ¹H NMR measurements confirm the formation of an unstable bimetallic intermediate, [(H)(PPh₃)₃Rh(μ-CO)₂Fe(CO)₄], characterized with ν_CO at 1749 cm⁻¹ and hydrido signal at δ ™15.8 ppm. This revised version was published online in August 2006 with corrections to the Cover Date.     

Z型g-C3N4/WO3·H2O的制备与光催化二氧化碳还原性能

利用可见光将CO₂转化为CO和CH₄有望同时解决温室效应和能源危机。Z型光催化体系能够最大限度降低光生电子-空穴对的复合,提高光催化效率。本文采用水热合成法制备了g-C₃N₄/WO₃·H₂O (CNW-1)复合材料,通过X射线衍射、X射线光电子能谱、电镜等方法进行结构表征,探究了298 K、0.1 MPa条件下其对CO₂的可见光催化还原性能,并提出了可能的反应机理。通过调控三氧化钨结晶水含量可以实现CO和CH₄的产量调节,在反应10 h后,CNW-1具有最高的CH₄产率(0.33 μmolg^_-1),而CNW具有最高的CO产率(0.67 μmolg_-1⁾。这项研究为CO₂选择性还原为C1化合物提供了一种有效策略,同时也突出了以g-C₃N₄作为半导体构建Z型光催化体系在催化领域的应用潜力。     

PIN/PAN聚合物基电解质膜的制备及性能

利用静电纺丝技术制备了聚吲哚/聚丙烯腈(PIN/PAN)聚合物基电解质膜,代替纸基铝空气电池中的纤维素纸(C-P),并应用于固态铝空气电池。探究了PIN含量对电解质膜离子电导率及吸液率的影响。采用SEM和FTIR对PIN/PAN聚合物基电解质膜表面形貌及化学组成进行分析。借助电化学工作站和电池测试系统,分析了电解质膜离子电导率及固态铝空气电池放电特性。结果表明,采用PIN/PAN聚合物基电解质膜可有效提升固态铝空气电池性能,在3 mA.cm_^-2、5 mA.cm_^-2、7 mA.cm_^-2电流密度下,放电时长比纸基铝空气电池分别提升了21%、27%、34%,且放电时长与电解质膜的吸液率及离子电导率相关。其中4%PIN/PAN聚合物基电解质膜离子电导率可达6.7×10_^-4 S.cm_^-1,同时对碱性溶液具有良好的吸附能力,吸液率最高可达496%,为纤维素纸的3.2倍。     

Characteristics of methane oxidation in a flooded rice soil profile

Laboratory experiments were conducted to study the variation of CH₄ oxidation patterns in flooded rice soil profiles. The results indicated that surface soil presented the strongest CH₄ oxidation activities as shown by the highest values of the two kinetic parameters of CH₄ oxidation, V_max and K_m in the ecosystem without rice plants. V_max and K_m decreased significantly from top to bottom in the paddy rice soil profile, ranging from 12.5 to 1.2 μg h^-1 g^-1 and 165 to 4.1 μg g^-1, respectively. In addition, we studied the effect of headspace N₂, O₂ and their ratio on CH₄ emission and oxidation to provide information on the sensitivity of methanogens and methanotrophs to soil redox change resulted from gas transportation through arenchyma. Methane emission rate increased, however, CH₄ oxidation rate decreased with a decrease of O₂ concentration in the headspace. Headspace H₂ increased CH₄ emission rate substantially. In addition to H₂ being a substrate for CH₄ formation, the change of soil redox potential to a considerably low level H₂ should also contribute to the increase in CH₄ emission. This revised version was published online in August 2006 with corrections to the Cover Date.     

NiPd/TiO2催化剂的制备及其催化甲酸分解制氢性能

高效、清洁且无毒无害的催化剂是实现以甲酸(HCOOH)为化学储氢材料分解制氢的重点。本文采用水热法在453K的条件下制备TiO₂载体,再通过浸渍法向其中加入总量为0.1 mmol的NiCl₂.6H₂O和K₂PdCl₄金属溶液,将活性组分Ni、Pd负载到TiO₂载体上合成NiPd/TiO₂催化剂,并探究其对催化甲酸分解制氢的性能的影响。探究结果表明,在光照条件下,NiPd/TiO₂催化剂中,当金属Ni:Pd比例为2:8时,催化剂的反应转化频率(TOF)值最大,此时催化剂的 TOF 为3528 h_-1^,且该催化剂上甲酸分解的活化能(E_a)为53.9 kJ/mol。关键词：镍钯催化剂;甲酸;分解制氢;二氧化钛;光照中图分类号：TQ630 文献标识码： A 文章编号：     

Ni/SiO2催化剂的2-MF加氢性能研究

本研究以硝酸镍为镍源,酸/碱性硅溶胶为硅源,采用共沉淀法制备了Ni/SiO₂催化剂。采用固定床反应器,评价Ni/SiO₂催化剂对于2-甲基呋喃(2-MF)气相加氢合成2-甲基四氢呋喃(2-MTHF)的反应性能。通过XRD、N₂等温吸附-脱附、H₂-TPR、NH₃-TPD、XPS、FT-IR和TEM等方法对催化剂结构进行表征,研究硅溶胶的酸碱性对Ni/SiO₂催化剂结构及性能的影响。结果表明：以酸性硅溶胶为硅源制备的Ni/SiO₂催化剂弱酸中心酸量多并且存在中强酸性中心,比表面积高,平均孔径大,因而该催化剂活性和2-MTHF的选择性高。Ni/SiO₂催化剂稳定性良好,在90 ℃,2 MPa,WHSV=4.4 h_?¹条件下连续反应200 h,2-MTHF的收率均保持在95.7%。关键词：2-甲基四氢呋喃;2-甲基呋喃;共沉淀法;Ni/SiO₂;酸碱性     

2D/2D WO3/Ag:ZnIn2S4 Z型异质结复合物的构筑及可见光催化性能

构筑Z型异质结复合物是光催化领域解决电子-空穴对复合较快的常用方法,其独特的双光子体系能高效的提升光催化速率而备受关注。本文通过水热法原位构筑二维/二维(2D/2D)WO₃/Ag:ZnIn₂S₄ Z型异质结复合物,并且利用透射电子显微镜(TEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)、紫外-可见漫反射光谱(UV-Vis DRS)、光电化学(PEC)和荧光光谱(PL)对其微观形貌、物相结构、元素化学态和光电性能等进行表征分析,以及采用可见光(加λ>420 nm的滤光片)照射来评价2D/2D WO₃/Ag:ZnIn₂S₄ Z型异质结复合物光解水制氢气和光降解甲基橙(MO)的催化性能。结果表明,在2D/2D WO₃/Ag:ZnIn₂S₄ Z型异质结复合物中,随着Ag:ZnIn₂S₄的含量增加,光催化性能也显著增强。当Ag:ZnIn₂S₄的质量分数为35.0%时,复合物表现出最佳的制氢速率(158.93 μmol.g_-1^.h_-1⁾与降解速率(0.18 min_-1^),这为基于WO₃纳米片设计和构筑2D/2D Z型异质结复合物用于可见光催化制氢和污染物降解提供了新的见解。     

Production of highly porous carbon sorbents for methane storage from coal, coke, and individual organic compounds

Highly porous carbon sorbents for methane storage are produced from coal, coke, and individual organic compounds. A static high-pressure volumetric system is used to establish the dependence of the methane and hydrogen adsorption on the micropore volume in the sorbents. The mean specific adsorption of CH₄ and H₂ at 60 atm (6 MPa) and 300 K is ～150 and ～6.5 mg/cm³, respectively. The results confirm physical adsorption of the gases (CH₄ and H₂).     

Catalytic filamentous carbon: Structural and textural properties

Catalytic filamentous carbon (CFC) synthesized by the decomposition of methane over iron subgroup metal catalysts (Ni, Co, Fe or their alloys) is a new family of mesoporous carbon materials possessing the unique structural and textural properties. Microstructural properties of CFC (arrangement of the graphite planes in filaments) are shown to depend on the nature of catalyst for methane decomposition. These properties widely vary for different catalysts: the angle between graphite planes and the filament axis can be 0° (Fe-Co-Al₂O₃), 15° (Co-Al₂O₃), 45° (Ni-Al₂O₃), 90° (Ni-Cu-Al₂O₃). The textural properties of CFC depend both on the catalyst nature and the conditions of methane decomposition (T, °C). The micropore volume in CFC is very low, 0.001-0.022 cm³ g⁻¹ at the total pore volume of 0.26-0.59 cm³ g⁻¹. Nevertheless, the BET surface area may reach 318 m² g⁻¹. Results of the TEM (HRTEM), XRD, Raman spectroscopic, SEM and adsorption studies of the structural and textural properties of CFC are discussed.     

One-pot synthesis of mesoporous SBA-15 containing protonated 3-aminopropyl groups

A new technique of synthesis of mesoporous silica with protonated amino groups avoiding microwave treatment of mesophase was developed using a template method. The block-copolymer P123 was used as a template and sodium meta-silicate with 3-aminopropyltriethoxysilane as precursors. After the removal of template from mesophase with boiling ethanol, the obtained sample displayed highly ordered hexagonal structure with attractive textural parameters: S_BET = 460 m² g^?1, V_total = 0.79 cm³g^?1 and d = 7.1 nm. FTIR and ¹³C CP/MAS NMR spectroscopy revealed the presence of alkyl ammonium groups (0.7 mmol g^?1) that were able to attach anions of molybdophosphoric acid to the surface of the synthesized mesoporous material. The resulting anion-ion exchange phase can find applications in many areas (adsorption, catalysis, etc.).     

Microporous polymelamine network for highly selective CO2 adsorption

Microporous polymelamine network was prepared through one-pot catalyst-free polymerization using the Schiff base reaction. Gas adsorption experiments indicate that the network possesses high CO₂ uptake capacity, reaching 89.0 cm³ g^?1 (17.9 wt%) at 1.0 bar and 273 K, along with high selectivity towards CO₂ over N₂ and CH₄. The porous polymeric network presents a promising potential as efficient adsorbents in clean energy applications.     

Gas storage scale-up at room temperature on high density carbon materials

In relation to the current interest on gas storage demand for environmental applications (e.g., gas transportation, and carbon dioxide capture) and for energy purposes (e.g., methane and hydrogen), high pressure adsorption (physisorption) on highly porous sorbents has become an attractive option. Considering that for high pressure adsorption, the sorbent requires both, high porosity and high density, the present paper investigates gas storage enhancement on selected carbon adsorbents, both on a gravimetric and on a volumetric basis. Results on carbon dioxide, methane, and hydrogen adsorption at room temperature (i.e., supercritical and subcritical gases) are reported. From the obtained results, the importance of both parameters (porosity and density) of the adsorbents is confirmed. Hence, the densest of the different carbon materials used is selected to study a scale-up gas storage system, with a 2.5 l cylinder tank containing 2.64 kg of adsorbent. The scale-up results are in agreement with the laboratory scale ones and highlight the importance of the adsorbent density for volumetric storage performances, reaching, at 20 bar and at RT, 376, 104, and 2.4 g l⁻¹ for CO₂, CH₄, and H₂, respectively.     

Superhydrophobic zeolitic imidazolate framework with suitable SOD cage for effective CH4/N2 adsorptive separation in humid environments

Various adsorbents for CH₄/N₂ separation were developed to enrich low-concentration coal-mine methane. Most are hydrophilic and cannot treat moist coal-mine methane. We report for the first time a microporous zeolitic imidazolate framework Co(dcIm)₂ (TUT-100) with superhydrophobic properties for CH₄/N₂ separation. The CH₄ adsorption capacity and CH₄/N₂ selectivity were as high as 45.29 cm³/cm³ and 6.3 (298 K, 1 bar), respectively, which results from the suitable SOD cage size (0.80 nm). The H₂O adsorption was lower than 6.3 cm³/g at 298 K and near saturated pressure due to the hydrophobic group  Cl. Breakthrough experiments were carried out to indicate the significant potential for CH₄/N₂ adsorption separation in a humid environment. The adsorption behavior of the gas mixture on the TUT-100 was investigated by the Grand Canonical Monte Carlo method and coupled with the experimental data.     

Heazlewoodite,Ni3S2: An electroactive material for supercapacitor application

Engineering of nanostructured materials with a unique and uniform morphological design is considered to be a competent candidate for a diverse range of electrochemical energy applications. However, the construction of ball-in-ball transition metal sulfide via the vaporization process remains a big challenge of today's research community. In this work, carbon encapsulated nickel sulfide (Ni₃S₂@C) with a complex hollow interior was synthesized and further studied with nitrogen-doped carbon encapsulated nickel sulfide (Ni₃S₂@NC) for comparison basis. We used metal salt (nickel nitrate) and organic linker (trimesic acid, TMA) as a precursor to synthesize Ni-TMA via a solvothermal method. Next, the sulfidation process was done under 5% H₂ balanced argon gas in a tubular furnace to convert into Ni₃S₂ with encapsulation of carbon. The prepared hybrid material showed ball-in-ball morphology and heazlewoodite mineral phase structure. Furthermore, the prepared materials were examined for electrochemical energy storage properties owing to their well-known faradaic dominant (battery-type) charge storage features and key positive electroactive material for today's growing hybrid electrochemical capacitor. The nitrogen-doped carbon encapsulated nickel sulfide has demonstrated good electrochemical features like a specific capacity of 442.45 F g^?1 at 5 mV s^?1 of scan rate and 373.52 F g^?1 at 2 A g^?1 of current density. Moreover, the material showed excellent capacitance retention of 81% and 70% after 5000 and 10,000 cycles run with 100% of coulombic efficiency at 8 A g^?1.     

Boosting C2H6/C2H4 separation in scalable metal-organic frameworks through pore engineering

The development of ethane (C₂H₆)-selective adsorbents for ethylene (C₂H₄) purification, although challenging, is of prime industrial importance. Pillared-layer metal-organic frameworks (MOFs) possess facilely tunable pore structure and functionality, which means they have excellent potential for high-performance C₂H₆/C₂H₄ separation applications. Herein, we report a family of isostructural pillared-layer MOFs with various metal centers M and co-ligands L, M₂(D-cam)₄L₂ (denoted M-cam-L; M = Cu, Co, Ni; L = pyz, apyz, dabco), with a variety of pore surface properties. All of the M-cam-L materials exhibit preferential adsorption for C₂H₆ over C₂H₄. In particular, Ni-cam-pyz exhibits the highest C₂H₆ capture capacity (68.75 cm³ g⁻¹ at 1 bar and 298 K), Cu-cam-dabco possesses the greatest C₂H₆/C₂H₄ adsorption selectivity (2.3), and the lowest isosteric heat of adsorption is demonstrated for Cu-cam-pyz (20.1 kJ mol⁻¹). Dynamic column breakthrough experiments also confirmed the excellent separation performance of M-cam-pyz and M-cam-dabco materials. The synthesis route of the M-cam-L materials is easily scaled-up under laboratory conditions, and hence this class of MOFs is promising for practical C₂H₄ purification.     

Simultaneous oxidative conversion and CO2 or steam reforming of methane to syngas over CoO–NiO–MgO catalyst

CO₂ reforming, oxidative conversion and simultaneous oxidative conversion and CO₂ or steam reforming of methane to syngas (CO and H₂) over NiO–CoO–MgO (Co: Ni: Mg=0·5: 0·5:1·0) solid solution at 700–850°C and high space velocity (5·1×10⁵ cm³ g⁻¹ h⁻¹ for oxidative conversion and 4·5×10⁴ cm³ g⁻¹ h⁻¹ for oxy-steam or oxy-CO₂ reforming) for different CH₄/O₂ (1·8–8·0) and CH₄/CO₂ or H₂O (1·5–8·4) ratios have been thoroughly investigated. Because of the replacement of 50 mol% of the NiO by CoO in NiO–MgO (Ni/Mg=1·0), the performance of the catalyst in the methane to syngas conversion process is improved; the carbon formation on the catalyst is drastically reduced. The CoO–NiO–MgO catalyst shows high methane conversion activity (methane conversion >80%) and high selectivity for both CO and H₂ in the oxy-CO₂ reforming and oxy-steam reforming processes at ⩾800°C. The oxy-steam or CO₂ reforming process involves the coupling of the exothermic oxidative conversion and endothermic CO₂ or steam reforming reactions, making these processes highly energy efficient and also safe to operate. These processes can be made thermoneutral or mildly exothermic or mildly endothermic by manipulating the process conditions (viz. temperature and/or CH₄/O₂ ratio in the feed). © 1998 Society of Chemistry Industry