Adsorption behavior of CO_(2)/H_(2)S mixtures in calcite slit nanopores for CO_(2) storage:An insight from molecular perspective

It is acknowledged that injecting CO_(2) into oil reservoirs and saline aquifers for storage is a practical and affordable method for CO_(2) sequestration.Most CO_(2) produced from industrial exhaust contains impurity gases such as H_(2)S that might impact CO_(2) sequestration due to competitive adsorption.This study makes a commendable effort to explore the adsorption behavior of CO_(2)/H_(2)S mixtures in calcite slit nanopores.Grand Canonical Monte Carlo(GCMC)simulation is employed to reveal the adsorption of CO_(2),H_(2)S as well as their binary mixtures in calcite nanopores.Results show that the increase in pressure and temperature can promote and inhibit the adsorption capacity of CO_(2) and H_(2)S in calcite nanopores,respectively.CO_(2)exhibits stronger adsorption on calcite surface than H_(2)S.Electrostatic energy plays the dominating role in the adsorption behavior.Electrostatic energy accounts for 97.11%of the CO_(2)-calcite interaction energy and 56.33%of the H_(2)S-calcite interaction energy at 10 MPa and 323.15 K.The presence of H_(2)S inhibits the CO_(2) adsorption in calcite nanopores due to competitive adsorption,and a higher mole fraction of H_(2)S leads to less CO_(2) adsorption.The quantity of CO_(2) adsorbed is lessened by approximately 33%when the mole fraction of H_(2)S reaches 0.25.CO_(2) molecules preferentially occupy the regions near the po re wall and H_(2)S molecules tend to reside at the center of nanopore even when the molar ratio of CO_(2) is low,indicating that CO_(2) has an adsorption priority on the calcite surface over H_(2)S.In addition,moisture can weaken the adsorption of both CO_(2) and H_(2)S,while CO_(2) is more affected.More interestingly,we find that pure CO_(2) is more suitable to be sequestrated in the shallower formations,i.e.,500-1500 m,whereas CO_(2)with H_(2)S impurity should be settled in the deeper reservoirs.

Fine quantitative characterization of high-H2S gas reservoirs under the influence of liquid sulfur deposition and adsorption

In order to clarify the influence of liquid sulfur deposition and adsorption to high-H2S gas reservoirs,three types of natural cores with typical carbonate pore structures were selected for high-temperature and high-pressure core displacement experiments.Fine quantitative characterization of the cores in three steady states(original,after sulfur injection,and after gas flooding)was carried out using the nuclear magnetic resonance(NMR)transverse relaxation time spectrum and imaging,X-ray computer tomography(CT)of full-diameter cores,basic physical property testing,and field emission scanning electron microscopy imaging.The loss of pore volume caused by sulfur deposition and adsorption mainly comes from the medium and large pores with sizes bigger than 1000μm.Liquid sulfur has a stronger adsorption and deposition ability in smaller pore spaces,and causes greater damage to reservoirs with poor original pore structures.The pore structure of the three types of carbonate reservoirs shows multiple fractal characteristics.The worse the pore structure,the greater the change of internal pore distribution caused by liquid sulfur deposition and adsorption,and the stronger the heterogeneity.Liquid sulfur deposition and adsorption change the pore size distribution,pore connectivity,and heterogeneity of the rock,which further changes the physical properties of the reservoir.After sulfur injection and gas flooding,the permeability of TypeⅠreservoirs with good physical properties decreased by 16%,and that of TypesⅡandⅢreservoirs with poor physical properties decreased by 90%or more,suggesting an extremely high damage.This indicates that the worse the initial physical properties,the greater the damage of liquid sulfur deposition and adsorption.Liquid sulfur is adsorbed and deposited in different types of pore space in the forms of flocculence,cobweb,or retinitis,causing different changes in the pore structure and physical property of the reservoir.

Study of the reaction mechanism for preparing powdered activated coke with SO_(2)adsorption capability via one-step rapid activation method under flue gas atmosphere

In this study,the impact of different reaction times on the preparation of powdered activated carbon(PAC)using a one-step rapid activation method under flue gas atmosphere is investigated,and the underlying reaction mechanism is summarized.Results indicate that the reaction process of this method can be divided into three stages:stage I is the rapid release of volatiles and the rapid consumption of O_(2),primarily occurring within a reaction time range of 0-0.5 s;stage II is mainly the continuous release and diffusion of volatiles,which is the carbonization and activation coupling reaction stage,and the carbonization process is the main in this stage.This stage mainly occurs at the reaction time range of 0.5 -2.0 s when SL-coal is used as material,and that is 0.5-3.0 s when JJ-coal is used as material;stage III is mainly the activation stage,during which activated components diffuse to both the surface and interior of particles.This stage mainly involves the reaction stage of CO_(2)and H2O(g)activation,and it mainly occurs at the reaction time range of 2.0-4.0 s when SL-coal is used as material,and that is 3.0-4.0 s when JJ-coal is used as material.Besides,the main function of the first two stages is to provide more diffusion channels and contact surfaces/activation sites for the diffusion and activation of the activated components in the third stage.Mastering the reaction mechanism would serve as a crucial reference and foundation for designing the structure,size of the reactor,and optimal positioning of the activator nozzle in PAC preparation.

A functionalized activated carbon adsorbent prepared from waste amidoxime resin by modifying with H_(3)PO_(4) and ZnCl_(2) and its excellent Cr(Ⅵ)adsorption

With the application of resins in various fields, numerous waste resins that are difficult to treat have been produced. The industrial wastewater containing Cr(Ⅵ) has severely polluted soil and groundwater environments, thereby endangering human health. Therefore, in this paper, a novel functionalized mesoporous adsorbent PPR-Z was synthesized from waste amidoxime resin for adsorbing Cr(Ⅵ). The waste amidoxime resin was first modified with H3PO4 and ZnCl_(2), and subsequently, it was carbonized through slow thermal decomposition. The static adsorption of PPR-Z conforms to the pseudo-second-order kinetic model and Langmuir isotherm, indicating that the Cr(Ⅵ) adsorption by PPR-Z is mostly chemical adsorption and exhibits single-layer adsorption. The saturated adsorption capacity of the adsorbent for Cr(Ⅵ) could reach 255.86 mg/g. The adsorbent could effectively reduce Cr(Ⅵ) to Cr(Ⅲ) and decrease the toxicity of Cr(Ⅵ) during adsorption. PPR-Z exhibited Cr(Ⅵ) selectivity in electroplating wastewater. The main mechanisms involved in the Cr(Ⅵ) adsorption are the chemical reduction of Cr(Ⅵ) into Cr(Ⅲ) and electrostatic and coordination interactions. Preparation of PPR-Z not only solves the problem of waste resin treatment but also effectively controls Cr(Ⅵ) pollution and realizes the concept of “treating waste with waste”.

不同矿浆温度下Ca^(2+)、Mg^(2+)对黄铁矿可浮性的影响

这是一篇矿物加工工程领域的论文。通过单矿物浮选实验、浮选溶液化学、Zeta电位、XPS,研究了不同矿浆温度下Ca^(2+)、Mg^(2+)对黄铁矿浮选效果的影响机理,结果表明:低温能够明显抑制黄铁矿的浮选,且温度降低能够明显弱化Ca^(2+)、Mg^(2+)对黄铁矿浮选的抑制作用。当矿浆温度从20℃降至5℃时,矿浆中带电粒子运动速度减慢,Zeta电位增大,生成氢氧化钙镁沉淀的临界pH值增大,纯水矿浆中黄铁矿表面的FeO/OH的比例减小,Ca^(2+)、Mg^(2+)矿浆中黄铁矿表面FeO/OH含量的降低幅度减小,减少了黄铁矿表面的氧化程度和活性吸附位点,减少了Ca^(2+)、Ca(OH)+,Mg^(2+)和Mg(OH)+等离子在黄铁矿表面的吸附;但低温并不改变Ca^(2+)、Mg^(2+)在黄铁矿表面的存在形式和吸附状态,pH值为9时,钙镁均以Ca^(2+)、Ca(OH)+、Mg^(2+)、Mg(OH)+的形式存在并吸附在黄铁矿表面。

可生物降解Zn-2Ag-0.04Mg合金生物相容性及体内骨再生能力的动物实验研究

目的:采用动物实验的方式,分析可生物降解Zn-2Ag-0.04Mg合金生物相容性及体内骨再生能力。方法:将30只实验兔随机均分为Zn支架组、Zn-2Ag支架组和Zn-2Ag-0.04Mg支架组(每组10只),建立兔股骨缺损模型后,分别使用不同材料的支架固定,术后6周及术后6个月,取出部分大白兔股骨,使用Micro-CT对股骨远端入口周围直径为3 mm的区域进行扫描和三维重建,分析支架体内成骨性能,使用X线观察局部骨缺损愈合情况,并观察股骨组织学情况。结果:入组实验兔实验中未出现异常行为及死亡现象,伤口均愈合良好,无感染及渗出情况出现;二维和三维显微CT结果显示,Zn-2Ag-0.04Mg支架组的新生骨明显多于Zn支架组,Zn-2Ag-0.04Mg合金支架组的骨体积更大(P<0.05);Zn-2Ag-0.04Mg支架组的成骨指数也高于Zn支架组(P<0.05);术后6个月时,Zn-2Ag-0.04Mg组的支架比Zn组或Zn-2Ag组小(P<0.05);肝脏、肾脏和心脏的HE染色未检测到任何异常,证实了Zn-2Ag-0.04Mg合金支架的生物安全性。结论:Zn-2Ag-0.04Mg支架具有良好的生物相容性和体内骨再生能力,具有较好的临床应用前景。

部分浸泡再生混凝土Mg^(2+)-SO_(4)^(2-)-Cl^(-)复合盐侵蚀耐久性损伤特征与机制

为系统研究与揭示西北地区部分掩埋再生混凝土(RAC)结构耐久性损伤特征与机制,以浓度为20%的复合盐溶液为侵蚀介质,开展了14种掺辅助胶凝材料RAC部分浸泡于复合盐溶液的耐久性试验,综合分析RAC动弹性模量、宏观与微观形貌、侵蚀产物物相组成与相对含量的经时变化规律。部分浸泡RAC沿纵向高度分为饱和区、气-液两相界面区、水分传输区及干燥区。侵蚀初期气-液两相界面区损伤程度高于饱和区;侵蚀中后期饱和区的损伤持平或超过气-液两相界面区,水分传输区损伤初现。饱和区侵蚀状态由初期的化学侵蚀转变为中后期的化学-物理双重侵蚀,气-液两相界面区在侵蚀期间均呈现出化学-物理双重侵蚀。化学侵蚀产物为水镁石、硬石膏/石膏、钙矾石、Friedel盐及碱式氯化镁;物理结晶盐包含氯镁石、白钠镁矾、氯化钠、水合硫酸镁、Na_(2)SO_(4)及芒硝,各侵蚀产物与结晶盐的相对含量均随浸泡时间延长而改变。侵蚀后期,Na_(2)SO_(4)和芒硝相互转化使RAC物理力学性能急速退化。粉煤灰-矿渣复掺RAC抗侵蚀性能整体较好,粉煤灰-硅灰复掺最差,后者在浸泡时间180 d时抗压强度损失率高于60%。矿渣-硅灰-偏高岭土三掺RAC耐久性显著高于粉煤灰-矿渣-偏高岭土三掺,后者在侵蚀180 d时已经溃散。四掺辅助胶凝材料RAC性能衰减速度均匀,但抗侵蚀性能仍处于较低水平,相同浸泡时间下,其耐久性指标均与粉煤灰-矿渣复掺RAC差距较大。

Mg(OH)_(2)对磷酸镁水泥水化过程及性能的影响

磷酸镁水泥(MPC)的镁质原料主要为重烧MgO,由于制备重烧MgO需要高温煅烧,其使用成本和碳排放量过高。氢氧化镁(Mg(OH)_(2))的来源丰富,制取成本低廉且无污染、安全环保,如能大量采用对缓解使用成本和碳排放量过高这一问题具有重要意义。因此,本工作使用Mg(OH)_(2)代替部分重烧MgO,通过X射线衍射、热分析、扫描电镜和能谱分析等测试手段,研究其对MPC工作性能、水化过程、强度发展和微观结构的影响。结果表明,Mg(OH)_(2)的掺入加快了MPC的水化过程,浆体的流动度降低,凝结时间缩短,本工作通过水玻璃热处理改性等缓凝手段改善其工作性能。随着Mg(OH)_(2)的掺入,磷酸镁水泥的水化温度和pH值显著降低,水化28 d后的K-鸟粪石(K-struvite)结晶数量增多,抗压强度随Mg(OH)_(2)含量的增加而降低,当Mg(OH)_(2)掺量在50%以内时,其后期强度下降在15%的范围内,随Mg(OH)_(2)掺量增大,更多的水化产物是由Mg(OH)_(2)反应形成的,当Mg(OH)_(2)掺量为66.6%时,重烧MgO的反应率由平均值22%降低至7%。总而言之,采用大掺量Mg(OH)_(2)制备磷酸镁水泥具有可行性且能确保材料的后期力学性能满足工程应用的要求,对降低磷酸镁水泥使用成本和碳排放具有潜在的应用前景。

Mg对亚共晶Al-10Mg_(2)Si合金组织与力学性能的影响

研究了不同Mg含量对含10 mass%Mg_(2)Si的亚共晶Al-Mg-Si合金显微组织、拉伸性能和断裂行为的影响。结果表明:在合金中添加1.2~2.8 mass%的Mg能够减小初生α-Al枝晶的尺寸,适量的Mg明显地细化了合金中的Mg_(2)Si共晶相,并使其形貌由粗大的汉字状转变为短条状、颗粒状和纤维状。共晶Mg_(2)Si的细化归因于Mg原子团簇在其两侧的富集,抑制了共晶Mg_(2)Si的生长,促进了其生长方向的改变。适量的Mg的添加同时提高了合金的强度和塑性,添加2.8 mass%Mg的合金拉伸性能达到最高,抗拉强度、屈服强度和伸长率分别由未添加Mg的232.4 MPa、150.4 MPa和1.5%增加到322.0 MPa、270.4 MPa和6.1%,分别提高了38.6%、79.8%和306.7%。未添加Mg的合金的断裂机制为脆性断裂,添加2.8 mass%Mg的合金的断裂机制转变为韧性断裂。

选区激光熔化成形TiB_(2)/Al-Si-Mg大尺寸复杂构件

选区激光熔化(SLM)成形大尺寸复杂构件厚度多样、成形高度较高、方向复杂,需要研究构件微观组织均匀性和力学性能稳定性。本文以SLM成形TiB_(2)/Al-Si-Mg复合材料为研究对象,分析复合材料多级微观组织,对比不同成形厚度、高度、方向下复合材料的力学性能。结果表明:复合材料表现出熔池特征结构,细小等轴晶粒组织均匀分布且随机取向,纳米TiB_(2)颗粒在材料内部弥散分布。随成形厚度增加,复合材料伸长率保持稳定,抗拉强度受本征热处理影响略微增大;在不同成形高度下,复合材料抗拉强度和伸长率保持稳定;在不同成形方向下,复合材料抗拉强度保持稳定,伸长率受熔池结构影响在水平方向略高。基于以上结果,成功制备大飞机舱门铰链臂(588 mm×318 mm×470 mm)复杂结构件。

聚乙烯亚胺和Mg2+荧光增敏快速检测四环素类抗生素

四环素类抗生素(TCs)是一类广谱抗菌药物,被广泛应用于治疗人畜疾病且效果显著,但过度使用TCs造成其在动物性食品中的残留问题会对自然环境和人体健康造成严重的危害。因此,对食品环境中TCs的残留进行快速检测是十分必要的。迄今为止,对TCs在酸性溶液中荧光检测相关的研究报道较少。在弱酸性条件下,TCs属于弱荧光物质,但与富有氨基的阳离子表面活性剂聚乙烯亚胺(PEI)结合时,在370 nm的激发下,在525 nm处产生较强的绿色荧光;当TCs与PEI和二价金属镁离子(Mg^(2+))共存时,TCs的荧光强度被进一步增强。本研究利用PEI和Mg^(2+)在弱酸性条件下对TCs的协同荧光增敏效应,构建了一种快速、简单、高灵敏检测残留TCs的荧光检测法。实验结果表明:在最优检测条件下,该体系对TCs的定量线性检测范围为5 nmol/L~2μmol/L,其中,美他环素(MTC)、四环素(TC)、土霉素(OTC)的相关系数R^(2)分别为0.939,0.997和0.999,检出限(LOD)分别为3.6,2.7和4.8 nmol/L,均远低于中国和欧盟的限量标准。本方法对MTC、TC、OTC表现出很高的特异性,与常见的其他抗生素均不产生干扰。在实际的牛奶检测中,该体系对TCs的加标回收率为91.64%~104.05%,相对标准偏差为1.20%~10.62%。本方法可适用于酸性体系中残留TCs的分析,为水体和食品中残留TCs检测提供了一种新的依据和思路。

Mg在CO_(2)/Ar混合气体中的双反应区燃烧模型研究

Mg粉/CO_(2)是实现火星探测原位资源利用的理想推进剂。针对Mg颗粒在含CO_(2)混合大气中燃烧,基于火焰层假设,建立了Mg在CO_(2)/Ar混合气体中的双反应区燃烧模型,分析了Mg在CO_(2)/Ar燃烧过程中各组分质量分数、各组分流量、颗粒和火焰层的温度分布,研究了环境压强、CO_(2)质量分数、环境温度和颗粒粒径对燃烧特性的影响。结果表明:环境压强增大,颗粒温度增大、火焰层温度变化不大。在环境压强低于20 kPa时,火焰层半径随环境压强升高快速增大,颗粒燃烧时间随环境压强升高快速变短,随后都基本保持不变;CO_(2)质量分数增大,颗粒温度与火焰层温度升高、火焰层半径减小、颗粒燃烧时间缩短;环境温度增大,颗粒温度变化不大、火焰层温度升高、火焰层半径减小、颗粒燃烧时间延长;颗粒粒径增大,颗粒温度与火焰层半径变化不大、火焰层温度降低、颗粒燃烧时间延长。

掺Mg^(2+)的ZIF-8材料的制备及抗菌和促成骨性能研究

金属有机框架材料被广泛应用于种植体、骨修复等医疗领域。选用二甲基咪唑为有机配体,Mg^(2+)、Zn^(1+)为金属结节,通过溶剂热法在室温下成功合成纳米级Mg@ZIF-8有机框架材料。Mg@ZIF-8纳米颗粒为正十二面体结构,粒径为200~400 nm,具有Mg–N、Zn–N、C–N、C=C、C=N、C-H官能团,在酸性微环境下不稳定,以上物理表征与ZIF-8相似。抗菌实验结果表明:随着Mg^(2+)浓度的升高,Mg@ZIF-8对大肠杆菌的抗菌性能逐步提高,而且一定浓度的Mg^(2+)对金黄色葡萄球菌的抗菌性能也有所提高。体外矿化实验表明:Mg^(2+)能够促进钛片表面P、Ca的沉积。Mg@ZIF-8有机框架材料在植入物领域有良好的应用前景。

Mechanism of microarc oxidation on AZ91D Mg alloy induced byβ-Mg_(17)Al_(12) phase

This work proposed a strategy of indirectly inducing uniform microarc discharge by controlling the content and distribution ofβ-Mg_(17)Al_(12)phase in AZ91D Mg alloy.Two kinds of nano-particles(ZrO_(2)and TiO_(2))were designed to be added into the substrate of Mg alloy by friction stir processing(FSP).Then,Mg alloy sample designed with different precipitated morphology ofβ-Mg_(17)Al_(12)phase was treated by microarc oxidation(MAO)in Na_(3)PO_(4)/Na2SiO3electrolyte.The characteristics and performance of the MAO coating was analyzed using scanning electron microscopy(SEM),energy dispersive spectrometer(EDS),X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),contact angle meter,and potentiodynamic polarization.It was found that the coarseα-Mg grains in extruded AZ91D Mg alloy were refined by FSP,and theβ-Mg_(17)Al_(12)phase with reticular structure was broken and dispersed.The nano-ZrO_(2)particles were pinned at the grain boundary by FSP,which refined theα-Mg grain and promoted the precipitation ofβ-Mg_(17)Al_(12)phase in grains.It effectively inhibited the“cascade”phenomenon of microarcs,which induced the uniform distribution of discharge pores.The MAO coating on Zr-FSP sample had good wettability and corrosion resistance.However,TiO_(2)particles were hardly detected in the coating on TiFSP sample.

基于阴极沉积Mg(OH)_(2)薄膜的镁合金超疏水表面改性及其耐蚀性研究

为延长镁合金的使役寿命,通过阴极沉积和超疏水改性在ME20M稀土镁合金表面制备超疏水涂层,采用硬脂酸乙醇基溶液对阴极沉积Mg(OH)_(2)薄膜的镁合金进行化学修饰,通过单因素试验分别考察硬脂酸浓度、溶液温度、浸泡时间对表面润湿性的影响规律,确定最优修饰工艺。对典型试样,采用点滴实验、全浸腐蚀实验及现代电化学测试技术评估其耐蚀性,采用划格法评价膜/基结合力,采用SEM、FT-IR及XRD分析试样表面微观形貌及成分。结果表明:阴极沉积Mg(OH)_(2)薄膜经低浓度硬脂酸溶液短暂浸泡即可获得超疏水性,蒸馏水静态接触角SCA高达151.5°,滚动角SA低至1.0°,呈低黏性。阴极沉积/疏水改性复合处理可显著改善镁合金的耐蚀性,与空白试样相比,复合处理试样的点滴液变色时间延长近25倍,在3.5%NaCl溶液中的自腐蚀电流密度Jcorr降低3个数量级,特征阻抗模值|Z|_(0.1 Hz)提高4个数量级。经疏水处理的阴极沉积Mg(OH)_(2)薄膜呈刀片状微纳结构,试样的红外光谱中出现明显的-CH_(3)和-CH_(2)-吸收峰。

多酸修饰的CuBi_(2)O_(4)/Mg-CuBi_(2)O_(4)同质结光阴极用于高效光电化学转化

CuBi_(2)O_(4)作为最有前景的光阴极材料之一,其理论光电流密度可达20 mA·cm^(-2)。然而,在实际光电化学反应中,由于光生载流子复合严重,实际的光电流密度相较于理论值仍然存在显著差异。一般而言,光电化学性能在很大程度上依赖于光生载流子的高效分离和传输,以及快速的反应动力学。本文中,我们提出了一种多金属氧酸盐(多酸)修饰的CuBi_(2)O_(4)/MgCuBi_(2)O_(4)同质结光阴极。系统考虑了光阴极体相和界面的载流子传输:首先,通过CuBi_(2)O_(4)/Mg-CuBi_(2)O_(4)同质结中所构造的内建电场实现光生电子和空穴的定向转移;另外,多酸助催化剂Ag6[P_(2)W_(18)O_(62)](AgP_(2)W_(18))在反应过程中可被还原,进而可被用作质子存储载体,可在抑制载流子复合的同时促进界面光电化学反应。这种协同作用可在促进体相-界面载流子传输的同时解决界面缓慢反应动力学这一瓶颈。结果表明,本文所提出的光阴极实现了出色的光电化学性能,在0.3 V vs.RHE时,光电流密度达-0.64 mA·cm^(-2);而在使用H2O2电子牺牲剂后,相同电位下的光电流密度进一步提升到-3 mA·cm^(-2)。本文所提出的光阴极与已有研究工作中报道的最佳结果相比,具有相当的光电化学活性,证明了其在实际应用中的巨大潜力。

二维层状麦克烯材料Nb_(2)C催化改性Mg(BH_(4))_(2)储氢性能研究

硼氢化镁(Mg(BH_(4))_(2))因具有14.9%的储氢量,被认为是一种具有良好前景的高容量储氢材料.考虑到二维层状过渡金属碳化物麦克烯材料(MXene)对Mg(BH_(4))_(2)的放氢过程具有显著的催化效果,文中采用酸刻蚀法制备了微观表征为二维层状的MXene材料碳化铌(Nb_(2)C),并通过机械球磨法将所制备的Nb_(2)C掺杂到Mg(BH_(4))_(2)中,以此来催化改性Mg(BH_(4))_(2)的放氢性能.由程序控温放氢(TPD)测试可得:在Mg(BH_(4))_(2)-x%Nb_(2)C(x=20,30,40)催化改性体系中,当x=40时,Mg(BH_(4))_(2)-40%Nb_(2)C体系的起始放氢温度可降至130℃左右,且升温至500℃后,可释放出12.8%H_(2),而未添加Nb_(2)C的纯Mg(BH_(4))_(2)约在285℃才开始放氢.除此之外,该体系在等温放氢测试中也表现出良好的放氢动力学性能,且由该体系改性后的放氢动力学性能可以在随后的第二和第三次吸放氢循环中保留下来,表现出良好的循环性能.

孔结构在MgFe_(2)O_(4)改性活性炭脱硫过程中的作用

合成了一系列MgFe_(2)O_(4)基改性球形活性炭吸附剂,用于室温下去除加湿空气中的H_(2)S,同时研究了孔隙结构对吸附性能的影响。通过SEM-EDS、氮气吸附-脱附和XRD对材料进行表征。结果表明,样品MFOR2-20对H_(2)S的吸附性能最好,达到204 mg/mL(571 mg/g);脱硫过程中形成的FeOOH作为中间体起到催化作用;产物包括单质硫和硫酸盐。H_(2)S的脱除包括吸附和催化氧化2种方式,H_(2)S的催化氧化一直持续到催化剂的所有有效孔被氧化产物堵塞。较小的孔隙可以增强催化剂的分散性、提供吸附中心并储存氧化产物。

Mg_(3)Sb_(2)合金中Mg空位对电子传输性能的影响

Mg_(3)Sb_(2)基合金因具有极低的本征晶格热导率而成为极具潜质的中温区热电材料之一,但其较低的载流子浓度和电导率是目前亟待解决的问题,除了常用的元素掺杂外,有望通过引入Mg空位来提高合金的p型传输倾向,从而成为解决这一问题的有效方法。基于此,本工作采用第一性原理计算方法对不同位置Mg的空位形成能和电子结构等参数进行了计算。由结果可知,Mg1位的Mg 2+阳离子空位更容易形成,且空位含量最高可达0.05,Mg空位的存在也有利于禁带中的Fermi能级向价带方向偏移,使得载流子浓度大幅提升。利用定向凝固方法制备了相同成分的合金并对其热电性能参数进行了测试,所得的电子传输性能变化趋势与计算预测结果一致,Mg 2.975 Sb_(2)合金的电导率和功率因子最大值分别为110 S·cm^(-1)和1.89 W·m^(-1)·K^(-1)。此外,Mg空位的存在导致的点缺陷也有利于声子的散射和晶格热导率的降低,使得780 K时Mg 2.975 Sb_(2)合金的最高热电优值达到0.49。本工作通过对Mg空位的调控使p型Mg_(3)Sb_(2)合金的电子传输性能得到提升,同时也为此类合金的热电性能优化提供了新的思路。

Mg-doped SrTaO_(2)N as a visible-light-driven H_(2)-evolution photocatalyst for accelerated Z-scheme overall water splitting

Perovskite SrTaO_(2)N is one of the most promising narrow-bandgap photocatalysts for Z-scheme overall water splitting.However,the formation of defect states during thermal nitridation severely hinders the separation of charges,resulting in poor photocatalytic activity.In the present study,we successfully synthesize SrTaO_(2)N photocatalyst with low density of defect states,uniform morphology and particle size by flux-assisted one-pot nitridation combined with Mg doping.Some important parameters,such as the size of unit cell,the content of nitrogen,and microstructure,prove the successful doping of Mg.The defect-related carrier recombination has been significantly reduced by Mg doping,which effectively promotes the charge separation.Moreover,Mg doping induces a change of the band edge,which makes proton reduction have a stronger driving force.After modifying with the core/shell-structured Pt/Cr_(2)O_(3)cocatalyst,the H_(2)evolution activity of the optimized SrTaO_(2)N:Mg is 10 times that of the undoped SrTaO_(2)N,with an impressive apparent quantum yield of 1.51%at 420 nm.By coupling with Au-FeCoO_(x)modified BiVO_(4)as an O_(2)-evolution photocatalyst and[Fe(CN)_(6)]_(3)−/[Fe(CN)_(6)]_(4)−as the redox couple,a redox-based Z-scheme overall water splitting system is successfully constructed with an apparent quantum yield of 1.36%at 420 nm.This work provides an alternative way to prepare oxynitride semiconductors with reduced defects to promote the conversion of solar energy.