Promoted hydrolysis performances and mechanism of Si-NaBH4-AlCl3 in deionized water

Si-based hydrolysis material system can be used in mobile/portable hydrogen source applications connected to fuel cells but is limited by alkaline solutions. In the present research, we reported an acid/alkaline free hydrolysis system combining silicon with NaBH₄. Samples with different ratios between Si and NaBH₄ are prepared via high energy ball milling and hydrolyzed in deionized water at different temperatures. Synergetic effect between silicon and NaBH₄ was found in the hydrolysis process. 2Si-NaBH₄ sample displays the best hydrolysis performances with the hydrogen yield of 1594 ml⋅g⁻¹ in deionized water at 70 °C. Thereafter, AlCl₃ is added into the 2Si-NaBH₄ sample to further improve its comprehensive properties. The effect of AlCl₃ content and promotion mechanism of the reaction are explored. 2Si-NaBH₄–5 wt% AlCl₃ sample shows a significant improvement with a high hydrogen yield of 1689 ml·g⁻¹ in deionized water at 70 °C and a corresponding conversion rate of 95.8%, indicating that the Si-NaBH₄-AlCl₃ composite is promising to be a hydrogen source in applications of mobile/portable fuel-cell-powered facilities.     

从土耳其Zonguldak鼠煤矿和西伯利亚无烟煤制备的几种活性炭的孔结构和氢吸附特性(英文)

Activated carbon samples were developed from coal samples obtained from a coal mine, rat (Zonguldak, Turkey) and anthracite (Siberia, Russia), applying pyrolysis in a temperature range of 600-900 ℃ under N2 flow, and activation using chemical agents such as KOH, NH4Cl, ZnCl2 at 650 ℃. Nitrogen adsorption at low temperature (77 K) was used to characterize the activated carbon samples, and their pore structure properties including pore volume, pore diameter and pore size distribution were determined by means ...     

污泥含炭吸附剂的制备及其吸附模拟烟气中汞蒸汽的应用(英文)

The carbonaceous adsorbent was prepared from mixtures of dewatered sludge and sawdust with enhanced ZnCl2 chemical activation.Characteristics of the adsorbent were studied using scanning electron microscope(SEM) ,Fourier transform infrared spectroscopy(FT-IR) ,and adsorption of nitrogen.The surface analysis showed that the carbonaceous adsorbent had good specific surface and porosity(394 m 2 ·g-1of BET surface,0.12 and 0.10 ml·g-1of microporous and mesoporous volume,respectively) .The oxygen functional groups such as OH,C O and C O were found on the surface by FTIR and XPS(X-ray photoelectron spectroscopy) .The adsorption of elemental mercury(Hg0) on the carbonaceous adsorbent was studied in a fixed bed reactor.The dynamic adsorption capacity of carbonaceous adsorbent increased with influent mercury concentration,from 23.6μg·g-1at 12.58μg·m-3to 87.9μg·g-1at 72.50μg·m-3,and decreased as the adsorption temperature increased,from 246 μg·g-1 at 25°C to 61.3μg·g-1 at 140°C,when dry nitrogen was used as the carrier gas.The carbonaceous adsorbent presented higher dynamic adsorption capacity than activated carbon,which was 81.2μg·g-1and 53.8μg·g-1respectively.The adsorption data were fitted to the Langmuir adsorption model.The physical and chemical adsorption were identified on the adsorbent.     

精细化工与催化 阳离子交换树脂改性及其在乙醇酸甲酯水解制备乙醇酸反应中的应用

采用AlCl₃和SnCl₄对苯乙烯系强酸性阳离子交换树脂进行改性,考察树脂改性条件对乙醇酸甲酯水解制备乙醇酸反应的影响,并优化水解工艺条件。结果表明,最佳树脂改性条件为:采用AlCl₃-SnCl₄等物质的量混合物联合改性,其添加量为树脂质量的8%~10%,改性水浴温度(70~75) ℃,改性时间(8~10) h;优化的乙醇酸甲酯水解制备乙醇酸的工艺条件为:空速(3~6) h^-1,水解温度(75~85) ℃,去离子水与乙醇酸甲酯物质的量比(10~20)∶1。经过300 h的稳定性实验表明,树脂改性后稳定性良好。     

Effects of electrodeposited Co and Co–P catalysts on the hydrogen generation properties from hydrolysis of alkaline sodium borohydride solution

Co and Co–P catalysts electroplated on Cu in sulfate based solution without or with an addition of H₂PO₂⁻ ions were developed for hydrogen generation from alkaline NaBH₄ solution. The microstructures of the Co and Co–P catalysts and their hydrogen generation properties were analyzed as a function of cathodic current density and plating time during the electrodeposition. An amorphous Co–P electrodeposit with micro-cracks was formed by electroplating in the sulfate based solution containing H₂PO₂⁻ ions. It was found that the amorphous Co–P catalyst formed at 0.01 A/cm² exhibited 18 times higher catalytic activity for hydrolysis of NaBH₄ than did the polycrystalline Co catalyst. The catalytic activity of the electrodeposited Co–P catalyst for hydrolysis of NaBH₄ was found to be a function of both cathodic current density and plating time, that is, parameters determining the concentration of P in the Co–P catalyst. Especially, Co–13 at.% P catalyst electroplated on Cu in the Co–P bath at a cathodic current density of 0.01 A/cm² for 1080 s showed the best hydrogen generation rate of 954 ml/min g-catalyst in 1 wt.% NaOH + 10 wt.% NaBH₄ solution at 30 °C.     

Homogeneous Co3O4 film electrode with enhanced oxygen evolution electrocatalysis via surface reduction

Homogeneous NaBH_4-reduced Co_O_4 thin film electrodes with enhanced oxygen evolution electrocatalysis were obtained via a controlled-synthesis route.Firstly CoOx colloids were synthesized via ethylene glycol solvothermal method and cast on conductive glass substrates.The oxygen evolution reaction(OER) electrocatalysis of these asprepared Co_3O_4 thin films were then significantly enhanced via a simple surface reduction by NaBH_4 solution.The OER catalytic performance of the NaBH_4-reduced thin films was strongly dependent on the NaBH_4 concentration.The use of NaBH_4-reduced thin film electrodes for OER in alkaline solution supported higher current density and consequently negative shifts of the onset potential compared to that of the pristine.The optimal B_(12.5,20)-Co_3O_4 thin films exhibited excellent OER catalytic performances:At the current density of 10 mA·cm~(-2),a low overpotential of 365 mV and a small Tafel slope of 59.0 mV·dec~(-1) were observed.In addition,these B_(12.5,20)-Co_3O_4 thin film electrodes possessed good stability that can well recover its OER performance in a 24-h chronoamperometric stability test.     

Engineering oxygen vacancy-rich Co3O4 nanowire as high-efficiency and durable bifunctional electrocatalyst for overall alkaline water splitting

A novel kind of vacancy-rich nanowire arrays were prepared by reducing rough Co₃O₄ nanowires with NaBH₄ solution on 3D nickel foam at room temperature for overall water splitting. Co₃O₄/NF treated by NaBH₄ for 10 min was highly active for oxygen evolution reaction (OER) and simultaneously efficient for hydrogen evolution reaction (HER) with the need of the overpotentials of 240 and 132 mV to drive 10 mA·cm^-2 in alkaline media, respectively. Furthermore, the electrocatalysts as both cathode and anode in a two-electrode system presented excellent durability for over 60 h at 10 mA·cm^-2, maintaining the cell voltage of merely 1.63 V. This work provides new methods and ideas for the preparation of transition metal oxide bifunctional electrocatalysts rich in oxygen vacancies.     

A facile preparation of hausmannite as a high-performance catalyst for toluene combustion

Mesoporous transition metal oxide catalysts are well-used in the elimination of volatile organic compounds. In this study, we developed an efficient method for the preparation of mesoporous-Mn₃O₄ (m-Mn₃O₄) without the use of templates or surfactants. In this method, KCl protects oxygen defects on the surface of fresh Mn₃O₄ crystallites. m-Mn₃O₄ shows higher ameliorative catalytic activity than bulk-Mn₃O₄ (b-Mn₃O₄) and calcined-Mn₃O₄ (c-Mn₃O₄), achieving toluene catalytic oxidation of T₁₀ and T₉₀ (the temperature at a conversion rate of about 10% and 90%) at 191 ℃ and 230 ℃, respectively (WHSV = 40,000 ml·g^-1·h^-1). Based on various characterizations, the prepared m-Mn₃O₄ has large specific surface area and abundant oxygen defects, and thus can provide more surface active sites, which give it superior toluene combustion activity.     

富氧空位Co3O4纳米线的制备及其电解水性能研究

在室温下利用NaBH₄溶液还原Co₃O₄纳米线获得富含氧空位（V_O）的三维自支撑纳米线阵列用作全水解电催化剂,其中NaBH₄处理10 min的Co₃O₄/NF在碱性介质中对析氧反应（OER）和析氢反应（HER）表现出很高的活性,在10 mA·cm^-2电流密度下分别仅需240和132 mV的过电位。V_O-Co₃O₄/NF同时作为阴极和阳极电催化剂时,在10 mA·cm^-2下电解水槽电压仅为1.63 V,其耐久性可达60 h以上。该工作为富含氧空位结构的过渡金属氧化物双功能电催化剂的制备提供了新的方法和思路。     

Cr掺杂的Co-B非晶态合金的制备及催化硼氢化钠水解制氢

采用化学还原法制备了三元非晶态Co-Cr-B纳米催化剂。采用透射电镜（TEM）、扫描电镜（SEM）、X射线衍射仪（XRD）等测试方法对催化剂的形貌、结构、成分做了表征。通过排水法进行NaBH₄溶液水解产氢反应,测量了催化剂的催化性能。结果表明,当掺杂少量的Cr时,催化剂的粒径明显减小,比表面积明显增大,催化剂的性能提高。过量的Cr会导致出现过多的氧化物和Cr ³⁺,覆盖了催化剂表面活性位点,降低催化剂的性能。当Cr与Co物质的量比为0.005时,催化剂性能最佳。与纯Co-B相比,其对硼氢化钠水解产氢速率提高了2倍。此外,研究了催化剂用量、NaBH₄浓度、反应温度、NaOH浓度等因素对NaBH₄溶液水解产氢反应的影响。     

CoB/CeO2催化剂的优化制备及在NaBH4液相制氢中的应用

为了提高硼氢化钠水解催化剂的活性与稳定性,本文采用化学还原和焙烧后处理制备了一系列CoB/CeO₂负载型催化剂,探究了该催化剂在NaBH₄液相释氢中的催化性能。通过扫描电镜、X射线衍射、X射线光电子能谱等表征手段分析了催化剂结构和组成,并结合催化剂在NaBH₄水解制氢中的催化活性,研究了不同焙烧后处理方式对CoB/CeO₂负载型催化剂体系的作用规律。结果表明CoB负载到CeO₂载体表面后催化剂仅呈现了CeO₂载体的萤石相结构,但针对活性组分对比分析表明在高温下（空气和氮气）仍然出现了CoB的显著晶化。CoB/CeO₂在空气和氮气焙烧气氛下都有利于提高CoB活性组分在CeO₂载体表面的固载强度,但是二者呈现出不同的微观形貌。在NaBH₄液相释氢中,CoB/CeO₂-air和CoB/CeO₂-N₂展示了显著不同的催化活性,并且随着焙烧温度的提高,二者催化性能差异更加明显,温度升高后CoB/CeO₂-air催化活性逐步降低,并在500℃左右完全失活,而CoB/CeO₂-N₂则呈现了趋于稳定的催化活性。     

Fabrication of Poly（y-glutamic acid）-coated Fe3O4 Magnetic Nanoparticles and Their Application in Heavy Metal Removal

In this study, poly（y-glutamic acid）-coated Fe3O4 magnetic nanoparticles （y-PGA/Fe304 MNPs） were successfully fabricated using the co-precipitation method. Fe3O4 MNPs were also prepared for comparison. The av erage size and specific surface area results reveal that 7-PGA/Fe304 MNPs （52.4 nm, 88.41 m2.g-1） have smaller particle size and larger specific surface area_ than Fe3O4 MNPs （62.0 nm, 76.83 mLg-1）. The y-PGA/Fe3O4 MNPs     

容量法测量5 A分子筛静态吸附CH4、CO和CO2的研究

采用容量法分别测量CH₄、CO和CO₂在5A分子筛上的等温吸附曲线,探究吸附温度和吸附压力对CH₄、CO和CO₂吸附量的影响。实验结果表明,吸附量随着吸附压力的上升逐渐增大。设定吸附温度在30 ℃、50 ℃和70 ℃时,5A分子筛在30 ℃时对CH₄吸附量最大,为13.60 cm³·g^-1;对CO和CO₂吸附量均在50 ℃时呈现最大值,分别为17.68 cm³·g^-1 和94.38 cm³·g^-1。而吸附温度70 ℃时,对3种气体的吸附量均减小。     

Mechanism and kinetics study on removal of Iron from phosphoric acid by cation exchange resin

Iron element is one of the main impurities in wet-process phosphoric acid and it has a significant impact on the subsequent phosphorus chemical products. This paper studied the feasibility of using Sinco-430 cation exchange resin for iron removal from phosphoric acid. The specific surface area and the total exchange capacity of resin were 8.91 m~2·g~(-1) and 5.18 mmol·g~(-1), respectively. The sorption mechanism was determined by FTIR and XPS and the results indicated that iron was combined with-SO_3 H in resin. The removal process was studied as a function of temperature, H_3 PO_4 content and mass ratio between resin and solution. The unit mass of resin to remove iron was 0.058 g·g~(-1) resin when the operating parameters were T = 50 ℃, H_3 PO_4 content = 27.61 wt%and S/L = 0.1, respectively. Kinetics study demonstrated that pseudo-second-order reaction model fits this study best and the calculated activation energy of overall reaction is 29.10 kJ·mol~(-1). The overall reaction process was mainly controlled by pore diffusion.     

A pillared-layer metal-organic framework for efficient separation of C3H8/C2H6/CH4 in natural gas

Metal-organic frameworks (MOFs) have great potentials as adsorbents for natural gas purification. However, the trade-off between selectivity and adsorption capacity remains a challenge. Herein, we report a pillared-layer metal-organic framework Ni(HBTC)(bipy) for efficiently separating the C₃H₈/C₂H₆/CH₄ mixture. The experimental results show that the adsorption capacity of C₃H₈ and C₂H₆ on Ni(HBTC)(bipy) are as high as 6.18 and 5.85 mmol·g^-1, while only 0.93 mmol·g^-1 for CH₄ at 298 K and 100 kPa. Especially, the adsorption capacity of C₃H₈ at 5 kPa can reach an unprecedented 4.52 mmol·g^-1 and for C₂H₆ it is 1.48 mmol·g^-1 at 10 kPa. The ideal adsorbed solution theory predicted C₃H₈/CH₄ selectivity is as high as 1857.0, superior to most of the reported materials. Breakthrough experiment results indicated that material could completely separate the C₃H₈/C₂H₆/CH₄ mixture. Therefore, Ni(HBTC)(bipy) is a promising material for separation of natural gas.     

加压微波辅助水解甘草酸粗品制备甘草次酸(英文)

A pressured microwave-assisted hydrolysis(PMAH) technique has been developed for hydrolyzing the crude glycyrrhizic acid(GA) extracted from licorice root to prepare glycyrrhetinic acid(GRA).In order to optimize the efficiency of PMAH,several experimental parameters were investigated,including liquid-solid ratio,hydrolysis time,sulfuric acid concentration and hydrolysis temperature.The optimized hydrolysis conditions were as follows:pressured microwave-assisted hydrolysis of crude GA for 21 min(taking 15 min to reach 150 oC,and holding it for 6 min) at 150 oC(at a radiation power of 450 W) in 3%-5% sulfuric acid solution with the liquid-solid(ml?g?1 crude GA) ratio of 25︰1.As a result of the considerable saving in time and higher product yields(up to 90%),PMAH was proved more effective than conventional methods.     

Facile synthesis of spinel LiNi0.5Mn1.5O4 as 5.0 V-class high-voltage cathode materials for Li-ion batteries

LiNi_0.5Mn_1.5O₄ and LiMn₂O₄ with novel spinel morphology were synthesized by a hydrothermal and post-calcination process. The synthesized LiMn₂O₄ particles (5-10 μm) are uniform hexahedron, while the LiNi_0.5Mn_1.5O₄ has spindle-like morphology with the long axis 10-15 μm, short axis 5-8 μm. Both LiMn₂O₄ and LiNi_0.5Mn_1.5O₄ show high capacity when used as cathode materials for Li-ion batteries. In the voltage range of 2.5-5.5 V at room temperature, the LiNi_0.5Mn_1.5O₄ has a high discharge capacity of 135.04 mA·h·g^-1 at 20 mA·g^-1, which is close to 147 mA·h·g^-1 (theoretical capacity of LiNi_0.5Mn_1.5O₄). The discharge capacity of LiMn₂O₄ is 131.08 mA·h·g^-1 at 20 mA·g^-1. Moreover, the LiNi_0.5Mn_1.5O₄ shows a higher capacity retention (76%) compared to that of LiMn₂O₄ (61%) after 50 cycles. The morphology and structure of LiMn₂O₄ and LiNi_0.5Mn_1.5O₄ are well kept even after cycling as demonstrated by SEM and XRD on cycled LiMn₂O₄ and LiNi_0.5Mn_1.5O₄ electrodes.     

Scalable synthesis of Na3V2(PO4)3/C with high safety and ultrahigh-rate performance for sodium-ion batteries

NASICON-type Na₃V₂(PO₄)₃ is a promising electrode material for developing advanced sodium-ion batteries. Preparing Na₃V₂(PO₄)₃ with good performance by a cost-effective and large-scale method is significant for industrial applications. In this work, a porous Na₃V₂(PO₄)₃/C cathode material with excellent electrochemical performance is successfully prepared by an agar-gel combined with freeze-drying method. The Na₃V₂(PO₄)₃/C cathode displayed specific capacities of 113.4 mAh·g^-1, 107.0 mAh·g^-1 and 87.1 mAh·g^-1 at 0.1 C, 1 C and 10 C, respectively. For the first time, the 500-mAh soft-packed symmetrical sodium-ion batteries based on Na₃V₂(PO₄)₃/C electrodes are successfully fabricated. The 500-mAh symmetrical batteries exhibit outstanding low temperature performance with a capacity retention of 83% at 0 ℃ owing to the rapid sodium ion migration ability and structural stability of Na₃V₂(PO₄)₃/C. Moreover, the thermal runaway features are revealed by accelerating rate calorimetry (ARC) test for the first time. Thermal stability and safety of the symmetrical batteries are demonstrated to be better than lithium-ion batteries and some reported sodium-ion batteries. Our work makes it clear that the soft-packed symmetrical sodium ion batteries based on Na₃V₂(PO₄)₃/C have a prospect of practical application in high safety requirement fields.     

Synthesis of hierarchical dendritic micro–nano structure ZnFe_2O_4 and photocatalytic activities for water splitting

Hierarchical dendritic micro–nano structure Zn Fe_2O_4 have been prepared by electrochemical reduction and thermal oxidation method in this work. X-ray diffractometry, Raman spectra and field-emission scanning electron microscopy were used to characterize the crystal structure, size and morphology. The results show that the sample(S-2) is composed of pure ZnFe_2O_4 when the molar ratio of Zn~(2+)/Fe~(2+)in the electrolyte is 0.35. Decreasing the molar ratio of Zn~(2+)/Fe~(2+), the sample(S-1) is composed of ZnFe_2O_4 and α-Fe_2O_3, whereas increasing the molar ratio of Zn~(2+)/Fe~(2+), the sample(S-3) is composed of ZnFe_2O_4 and Zn O. The lattice parameters of ZnFe_2O_4 are influenced by the molar ratio of Zn~(2+)/Fe: Zn at excess decreases the cell volume whereas Fe at excess increases the cell volume of Zn Fe_2O_4. All the samples have the dendritic structure, of which S-2 has micron-sized lush branches with nano-sized leaves. UV–Vis diffuse reflectance spectra were acquired by a spectrophotometer. The absorption edges gradually blue shift with the increase of the molar ratio of Zn~(2+)/Fe~(2+). Photocatalytic activities for water splitting were investigated under Xe light irradiation in an aqueous olution containing 0.1 mol·L~(-1)Na_2S/0.02 mol·L~(-1)Na_2SO_3 in a glass reactor. The relatively highest photocatalytic activity with 1.41 μmol·h-1· 0.02 g~(-1)was achieved by pure ZnFe_2O_4sample(S-2). The photocatalytic activity of the mixture phase of Zn Fe_2O_4 and α-Fe_2O_3(S-1) is better than ZnF e_2O_4 and ZnO(S-3).     

Reductant-assisted polydopamine-modified membranes for efficient water purification

Surface engineering with polydopamine coatings has been considered a promising surface functionalisation tool.However,it is difficult to control the self-polymerisation for polydopamine formation,which usually causes severe interparticle aggregation.In this study,polydopamine self-polymerisation was controlled by adjusting its reducing environment using a reductant(NaBH4)to fabricate mixed cellulose ester(MCE)/polydopamine membranes.An oxidising environment using NaIO4 was additionally tested as the control.The results showed that a thin polydopamine coating with small polydopamine particles was formed on the skeleton frameworks of the MCE membrane with NaBH4,and the self-polymerisation rate was suppressed.The polydopamine coating formed in the reducing environment facilitated excellent water transport performance with a water permeance of approximately 400 L·m^?2·h^?1·bar^?1 as well as efficient organic foulant removal with a bovine serum albumin rejection of approximately 90%.In addition,the polydopamine coating with NaBH4 exhibited both excellent chemical stability and anti-microbial activity,demonstrating the contribution of the reducing environment to the performance of the MCE/polydopamine membranes.It shows significant potential for use in water purification.