醋酸钙模板剂制备棉涤废料基介孔炭及其吸附水中四环素研究

以棉涤废料为炭前驱体,利用醋酸钙为模板剂,采用单因素法考察在不同热解温度、质量比和热解时间下制得的介孔炭对亚甲基蓝和四环素的吸附性能,从而筛选得到最佳制备工艺参数,同时利用氮气吸附−脱附曲线、扫描电镜、X射线衍射、红外光谱进行物化性能分析,并研究其对水中四环素的吸附规律。结果表明,制备棉涤废料基介孔炭的最佳工艺参数为：...     

巯基功能化介孔硅的孔径调节及其吸附性能研究

叙述了以F127和CTMABr为模板剂,添加扩孔剂1,3,5三甲苯（TMB）经水热法合成不同孔径的巯基（-SH）修饰的新型介孔吸附剂。指出,以Cu＋2和Pb＋2为处理对象,根据不同孔径的介孔吸附剂对重金属离子的吸附性能,确定扩孔剂TMB投加量为TMB和表面活性剂摩尔比为1.5时,可得到重金属吸附的适用吸附剂的扩孔功能化硅基介孔材料,其BET孔径为6.554 nm,BET孔容为0.6134 cm3/g。     

形貌可控介孔W-SBA15的制备及染料吸附性能研究

以钨酸钠为钨源,丙三醇为助溶剂,采用溶胶-凝胶法一步合成了W-SBA15介孔分子筛,借助X射线衍射、氮气吸附脱附、扫描电子显微镜和透射电子显微镜等表征手段分析了介孔材料的微观结构和孔隙结构。结果表明,制备的W-SBA15样品具有六方介孔结构,钨元素插入孔壁或形成三氧化钨微晶均匀分散在介孔孔道内。通过改变合成条件可以调控介孔材料的孔道长度。亚甲基蓝和罗丹明B的吸附测试结果表明,掺杂钨元素后,短孔道的介孔材料对两种染料的吸附能力均有所增强,但其吸附阴离子染料亚甲基蓝的能力增强得更为明显,这可能主要和染料的分子尺寸有关。     

磁性花椒树枝生物炭对Cr(Ⅵ)的吸附特性研究

原生花椒树枝生物炭(PB)对Cr(Ⅵ)的吸附能力有限(10.91 mg/g),且在反应结束后回收困难。文章通过使用浓度为0.4,0.6,0.8,1.0 mol/L的Fe(NO₃)₃溶液浸渍花椒树枝粉末,然后在500℃的温度下热解制备磁性花椒树枝生物炭(MZB)。通过SEM,XRD,FTIR和BET等表征分析,结合批式吸附试验,研究了MZB的理化特性和对Cr(Ⅵ)的吸附性能。研究结果表明：Fe₃O₄成功地附载在MZB上,与PB相比,MZB表面的羟基数量增多,比表面积和总孔容增大;MZB6对Cr(Ⅵ)的吸附效果最佳,可达32.3 mg/g,低pH值条件有利于MZB对Cr(Ⅵ)的吸附。Langmuir模型和伪二阶动力学模型的拟合结果表明,MZB对Cr(Ⅵ)的去除是通过均相化学吸附进行的。MZB6在第5次吸附-解吸循环后,对Cr(Ⅵ)的去除率仍能达到54%。     

B_(2)O_(3)包覆NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)正极材料制备及其电化学性能北大核心CSCD

O3型层状氧化物正极材料NaNi_(1/3)Mn_(1/3)Fe_(1/3)O_(2)具有高比容量、低成本和环境友好性等优点,被认为是最有前途的钠离子电池正极材料之一,但在充放电过程中会发生一系列复杂的相变,导致电化学性能较差。本研究报道了一种协同改性方法,以同时提高NaNi_(1/3)Mn_(1/3)Fe_(1/3)O_(2)正极材料的循环稳定性和倍率性能。通过将硼酸粉末和正极材料固相球磨混匀后低温煅烧,在NaNi_(1/3)Mn_(1/3)Fe_(1/3)O_(2)正极材料表面包覆纳米非金属氧化物B_(2)O_(3)。借助X射线衍射仪(XRD)、扫描电子显微技术(SEM)、透射电子显微镜(TEM)和电化学技术等测试手段,对比分析不同包覆量和原材料的形貌和电化学性能,筛选得到最优包覆量为2%(质量分数,余同)。该方法实现了B_(2)O_(3)的均匀包覆,并且没有改变NaNi_(1/3)Mn_(1/3)Fe_(1/3)O_(2)正极材料的晶体结构。通过电化学性能测试表明2%B_(2)O_(3)包覆材料在1 C倍率下循环200圈容量保持率从78%提升至87%。同时,2%B_(2)O_(3)包覆材料的高倍率性能也得到了改善,10 C高倍率下放电比容量从75 mAh/g提升至99 mAh/g。结果表明,这是一种有效且可靠的表面改性策略,可以增强钠离子电池层状氧化物正极材料的电化学性能。     

Mo,Al掺杂的Li_(7)La_(3)Zr_(2)O_(12)基复合固态电解质的制备及全固态电池性能研究北大核心CSCD

通过固态电解质构建的全固态锂离子电池具有极高的安全性及可靠性,是目前锂离子电池领域的研究热点。其中复合固态电解质既改善了聚合物电解质力学性能差、离子电导率低等缺点又解决了无机固态电解质的界面接触等问题。本文通过溶胶-凝胶法制备了掺杂了Al、Mo的Li_(7)La_(3)Zr_(2)O_(12)粉体,并将其与PEO(聚环氧乙烷)复合,利用溶液浇筑法制备了不同比例的复合固态电解质,考察其在全固态电池中的性能。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、差示扫描量热仪(DSC)等测试手段对Li_(6.65)Al_(0.05)La_(3)Zr_(1.9)Mo_(0.1)O_(12)粉体以及复合固态电解质进行了材料表征。同时利用电化学工作站、电池充放电测试系统测试了复合固态电解质在全固态电池中的应用性能。与纯PEO电解质相比,复合15%Li_(6.65)Al_(0.05)La_(3)Zr_(1.9)Mo_(0.1)O_(12)的电解质电化学窗口为4.79V,可以在0.2mA/cm^(2)下稳定循环500h,在0.1C倍率下,循环100圈容量保持率为89.9%。     

一步水热法制备三维石墨烯/Fe_(3)O_(4)复合材料及其储锂性能北大核心CSCD

Fe_(3)O_(4)作为锂离子电池负极材料,在充放电时体积变化较大,导致其容量衰减严重。目前,碳包覆是解决这个问题的主要方式之一。本工作以氧化石墨烯(GO)和Fe^(2+)为原料,用一步水热法合成了三维石墨烯片包覆Fe_(3)O_(4)纳米颗粒3DG@Fe_(3)O_(4)复合材料。使用傅里叶红外光谱(FT-IR)仪、热重分析(TGA)仪、X射线衍射(XRD)仪、拉曼光谱(Raman)仪、扫描电子显微镜(SEM)对复合物进行表征,研究结果表明,复合材料呈现石墨烯(G)片包覆Fe_(3)O_(4)纳米颗粒的三明治结构。同时采用了恒流充放电(GCPL)、循环伏安(CV)以及交流阻抗(EIS)等电化学测试方法,着重研究了Fe_(3)O_(4)含量对其电化学性能的影响,Fe_(3)O_(4)质量分数为83.2%的3DG@Fe_(3)O_(4)-2电极具有最高的比容量和循环性能,在0.1 A/g的电流密度下的首次放电比容量为1412.33 mAh/g,循环100次后的放电比容量为577 mAh/g,是纯Fe_(3)O_(4)电极材料经历100次循环后的6.5倍。一步水热合成方法具有操作简单、合成条件温和及无需额外添加还原剂等优点;制备的复合电极相比纯Fe_(3)O_(4)具有电极容量高、循环稳定性能好的优势,有助于推动Fe_(3)O_(4)基负极材料在电化学领域中的应用。     

简便制备三维多级Fe_(3)O_(4)/碳纳米纤维一体化电极及其储钠性能研究北大核心CSCD

作为钠离子电池负极材料之一的铁氧化物,其理论比容量高,但在循环过程中会发生较大的体积膨胀,表现出明显的容量衰减。以柔性碳基材料为基底原位构建纳米结构的金属氧化物可作为一种缓解其体积膨胀的有效手段。本文采用化学气相沉积法在泡沫铜上原位生长了多孔碳纳米纤维(CNFs),以此为柔性导电基底,通过盐溶液浸渍与退火相结合的简便方法制备得到三维多级Fe_(3)O_(4)/碳纳米纤维(3D Fe_(3)O_(4)/CNFs)一体化电极电极,并将其用作钠离子电池负极。使用X射线光电子能谱(XPS),拉曼光谱(Raman),扫描电子显微镜(SEM)对样品进行组分分析及形貌表征。使用恒流充放电(GCD),循环伏安(CV),电化学阻抗(EIS)对其进行电化学性能表征。结果表明,尺寸在50~100 nm的纳米棒状Fe_(3)O_(4)均匀分散在多孔碳纳米纤维上,构建出富含孔隙的三维多级结构。在0.1 A/g的电流密度下,3D Fe_(3)O_(4)/CNFs一体化电极经过100圈循环后,其比容量可达893.4 mAh/g,优于CNFs电极,并表现出更快的钠离子扩散动力学,同时具有较好的电化学可逆性。本文为金属氧化物/碳基复合电极研究提供了思路与实验依据。     

2021 年 1 期目录

以棉涤废料为炭前驱体,利用醋酸钙为模板剂,采用单因素法考察在不同热解温度、质量比和热解时间下制得的介孔炭对亚甲基蓝和四环素的吸附性能,从而筛选得到最佳制备工艺参数,同时利用氮气吸附?脱附曲线、扫描电镜、X射线衍射、红外光谱进行物化性能分析,并研究其对水中四环素的吸附规律。结果表明,制备棉涤废料基介孔炭的最佳工艺参数为：热解温度为800 ℃、醋酸钙和棉涤废料质量比为1.5∶1、热解时间为1.5 h。醋酸钙模板剂成孔性能优异,制得的介孔炭总比表面积高达1 106.630 m2·g?1,介孔率达到62%,对水中四环素的吸附过程符合Langmuir模型,为自发吸附,最大吸附值为506.40 mg·g?1。     

The modification of the mesoporous carbon CMK-3 with the aqua regia and its adsorption desulfurization mechanism

Ordered mesoporous carbon CMK-3 was synthesized and modified with aqua regia. Dibenzolthiophene (DBT) was employed to evaluate the adsorptive desulfurization performance of the adsorbents. It was found that such modification considerably enhanced the saturated sulfur capacity and breakthrough sulfur capacity toward DBT by 2 times, respectively. The modified CMK-3 possessed good reused performance. In order to make a deep study of main reasons for such increase, some characterizations including XRD, BET, TEM, FTIR, XPS, and Boehm titration were carried out. Based on the characterization results, the increased adsorption performance of modified CMK-3 was mainly attributed to the changes of the surficial acidic oxygen-containing functional groups. On such surface, the phenolic hydroxyl and the carboxyl groups have the chemical interactions with the S and the aromatic rings of DBT. Such interaction concerning the carboxyl groups devoted itself to the desulfurization more than the phenolic hydroxyl, and the cracking of the C-S bond of DBT also happen.     

Electrochemical supercapacitor behavior of Ni3(Fe(CN)6)2(H2O) nanoparticles

Nanosized Ni₃(Fe(CN)₆)₂(H₂O) was prepared by a simple co-precipitation method. The electrochemical properties of the sample as the electrode material for supercapacitor were studied by cyclic voltammetry (CV), constant charge/discharge tests and electrochemical impedance spectroscopy (EIS). A specific capacitance of 574.7 F g⁻¹ was obtained at the current density of 0.2 A g⁻¹ in the potential range from 0.3 V to 0.6 V in 1 M KNO₃ electrolyte. Approximately 87.46% of specific discharge capacitance was remained at the current density of 1.4 A g⁻¹ after 1000 cycles.     

First-principles study of H2 adsorption on the pristine and oxidized (8,0) carbon nanotube

The effect of oxygen, hydrogen, and (oxygen + hydrogen) molecules adsorption on the structural and electrical properties of (8,0) carbon nanotube (CNT) are investigated through density functional theory. The obtained results indicate endothermical chemisorption of O₂ on the nanotube surface with a large binding energy of about 598 meV and a significant charge transfer of about 0.43 e per molecule. It is discussed that the O₂ chemisorption creates hole carries in the (8,0) carbon nanotube and thus increases the work function of the system. In the case of hydrogen molecule, a weak physisorption on the surface of CNT (∼−5 meV) is identified. The adsorption of H₂ on CNT is also accompanied by hole doping and increment of the work function of the CNT, while the charge transfer between CNT and H₂ is negligible. The band offsets in the H₂-CNT junction are calculated to examine and describe the observed hole doping in this system. The effect of oxygenation of CNT on hydrogen adsorption is also investigated and the most favorable adsorption configuration is found and the related adsorption energy is calculated. It is argued that the oxygenation of CNT enhances the physisorption of hydrogen molecules. It is shown that hydrogen molecule adsorption on the oxidized CNT cancels hole doping and hence decreases the work function of the system.     

Preparation of a porous carbon from ferrocene-loaded polyaniline and its use in hydrogen adsorption

A porous carbon made of polyaniline with different ferrocene loadings was prepared through carbonization and thermal chemistry activation with KOH. The ferrocene served as a pore-forming agent and a resource of iron nanoparticles. N₂ adsorption/desorption measurements showed that the specific surface area and pore volume ranged from 2681 to 3246 m² g⁻¹ and from 1.56 to 2.06 cm³ g⁻¹, respectively, with increasing ferrocene loadings. Similarly, hydrogen adsorption also increased from 5.3 to 6.2 wt% at 77 K/5 MPa and 0.6 wt% to 0.85 wt% at 293 K/8 MPa. Scanning electron microscopy, X-ray diffraction and energy dispersive X-ray analysis showed that iron nanoparticles were embedded in the carbon matrix or dispersed on the surface. The large specific surface area and big pore volume improved the original hydrogen adsorption heat up to 7.2 kJ mol⁻¹ for the best sample.     

Synthesis and dehydrogenation of LiCa(NH2)3(BH3)2

We report the synthesis of a new hydrogen storage material with a composition of LiCa(NH₂)₃(BH₃)₂. The theoretical hydrogen capacity of LiCa(NH₂)₃(BH₃)₂ is 9.85 wt.%. It can be prepared by ball milling the mixture of calcium amidoborane (Ca(NH₂BH₃)₂) and lithium amide (LiNH₂) in a molar ratio of 1:1. The experimental results show that this material starts to release hydrogen at a temperature as low as ca. 50 °C, which is ca. 70 °C lower than that of pure Ca(NH₂BH₃)₂ possibly resulting from the active interaction of NH₂⁻ in LiNH₂ with BH₃ in Ca(NH₂BH₃)₂. ca. 4.1 equiv. or 6.8 wt.% hydrogen can be released at 300 °C. The dehydrogenation is a mildly exothermic process forming stable nitride products.     

Ab initio study of hydrogen adsorption on Zn2(NDC)2(diPyTz) metal-organic framework decorated with alkali and alkaline earth metal cations

We have studied effect of alkali and alkaline earth metal cations (Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺) decoration on hydrogen adsorption of the organic linker of Zn₂(NDC)₂(diPyTz) by employing three cluster models: diPyTz:mLi⁺ (m = 1–4), diPyTz:mLi⁺:nH₂ (m = 0,1,2 and n = 1–5) and diPyTz:1M⁺:1H₂ (M⁺ = Na⁺, K⁺, Be²⁺, Mg²⁺) complexes, using density functional theory (DFT) and second-order Moller–Plesset perturbation theory (MP2). The calculated binding energies show that decoration of the organic linker with alkali and alkaline earth metal cations enhanced H₂ interaction with diPyTz when compared with the pristine diPyTz. The atomic charges were derived by Mulliken, ChelpG and ESP methods. Finally, the atoms in molecules theory (AIM) were also applied to get more insight into the nature of the interaction of diPyTz and Li⁺. Results of AIM analysis show that N–Li⁺ bond in diPyTz organic linker's complex appears as shared electron interaction.     

铁改性活性炭对水中镉的吸附和再生实验研究

制备了铁改性活性炭,通过快速动态小柱实验研究了活性炭改性前后对镉的吸附性能,同时考察了进水pH、进水流量和初始质量浓度等因素对吸附材料穿透特性的影响,最后对铁改性活性炭再生方法进行了研究.结果表明,铁改性活性炭对镉的吸附量是未改性活性炭的3.7倍,负载的铁氧化物大大提高了改性活性炭对镉的吸附能力,同时铁改性活性炭对镉的吸附受溶液pH、进水流量和初始质量浓度的影响.0.05 mol·L-1的EDTA-2Na溶液能有效再生吸附饱和后的改性活性炭,再生后的改性活性炭可重复使用.     

Influence of the method of synthesis on hydrogen adsorption properties of mesoporous binary B2O3/Al2O3 gel systems

Three series of binary oxide systems B₂O₃/Al₂O₃ were prepared and the effect of alumina on dispersion of boron (B₂O₃) component was investigated. The aim of the study was to achieve a maximum dispersion of B₂O₃ in the Al₂O₃ a gel matrix that would lead to increased sorption capacity on boron oxide. Many attempts were made to establish the preparation conditions that would lead to a maximum dispersion of B₂O₃ in the Al₂O₃ gel matrix needed to increase the hydrogen sorption capacity on boron oxide. The systems were characterized by X-ray diffraction, SEM, TEM and low temperature nitrogen adsorption. Hydrogen adsorption was tested in the volumetric system.Results of the study showed that the amount of hydrogen adsorbed on B₂O₃ depended not only on the surface area of the system but also on the separation of B₂O₃ domains in Al₂O₃ gel network. Irrespective of the method of synthesis of the binary oxide system, the dispersion of B₂O₃ phase reflected in the amount of hydrogen adsorbed was the highest for the systems of the lowest B/Al molar ratios studied, i.e. for B/Al = 0.25.     

Synthesis and performance of Li3(V1−xMgx)2(PO4)3 cathode materials

In order to search for cathode materials with better performance, Li₃(V_1−xMg_x)₂(PO₄)₃ (0, 0.04, 0.07, 0.10 and 0.13) is prepared via a carbothermal reduction (CTR) process with LiOH·H₂O, V₂O₅, Mg(CH₃COO)₂·4H₂O, NH₄H₂PO₄, and sucrose as raw materials and investigated by X-ray diffraction (XRD), scanning electron microscopic (SEM) and electrochemical impedance spectrum (EIS). XRD shows that Li₃(V_1−xMg_x)₂(PO₄)₃ (x = 0.04, 0.07, 0.10 and 0.13) has the same monoclinic structure as undoped Li₃V₂(PO₄)₃ while the particle size of Li₃(V_1−xMg_x)₂(PO₄)₃ is smaller than that of Li₃V₂(PO₄)₃ according to SEM images. EIS reveals that the charge transfer resistance of as-prepared materials is reduced and its reversibility is enhanced proved by the cyclic votammograms. The Mg²⁺-doped Li₃V₂(PO₄)₃ has a better high rate discharge performance. At a discharge rate of 20 C, the discharge capacity of Li₃(V_0.9Mg_0.1)₂(PO₄)₃ is 107 mAh g⁻¹ and the capacity retention is 98% after 80 cycles. Li₃(V_0.9Mg_0.1)₂(PO₄)₃//graphite full cells (085580-type) have good discharge performance and the modified cathode material has very good compatibility with graphite.