负载铈-铜茶梗基生物炭联合脱硝除汞的性能研究

为了获得廉价易得的可以同时脱硝除汞的吸附催化剂,选取云南普洱茶废弃茶梗为碳源,采用等体积浸渍的方法制备了不同二氧化铈(CeO_2)-氧化铜(CuO)(CeO_2-CuO)浸渍配合比的茶梗基生物炭。并运用氮气(N_2)吸附脱附、扫描电子显微镜(SEM)、X射线衍射(XRD)对吸附催化剂进行了表征。在100~300℃范围内,固定床模拟烟气条件下研究了联合去除的效果。研究结果表明:CeO_2和CuO的浸渍量都为4%(wt,质量分数),制得的茶梗基生物炭,在300℃条件下,对一氧化氮(NO)的降解率达到82.3%,在100℃条件下,对单质汞(Hg0)的降解率高达93.0%。     

磁性硅铁载铜吸附Hg0动力学机制及密度泛函研究

采用粉末冶金法将纳米单质铜(Cu⁰)、硅铁(FeSi)、四氧化三铁硅涂层(Fe₃O₄@SiO₂)混合煅烧并制备出新型磁性硅铁载铜吸附剂MagFeSi-Cu⁰。实验研究不同烟气温度下MagFeSi-Cu⁰的汞吸附能力基础上,结合颗粒内扩散模型、准二阶动力学模型、Elovich模型及Bangham模型分析了MagFeSi-Cu⁰吸附Hg⁰过程的主要控制步骤。在此基础上,依据密度泛函理论(DFT)研究了不同反应温度下FeSi表面Cu⁰原子与Hg⁰原子的汞齐作用机制。研究结果表明,Bangham模型的拟合值与MagFeSi-Cu⁰汞吸附实验值拟合度最高,MagFeSi-Cu⁰表面痕量Hg⁰吸附由汞的外扩散和表面铜汞齐吸附共同控制;通过密度泛函计算,发现Cu⁰颗粒表面Cu-Hg齐吸附能为-0.534 eV,当烟气温度从80℃上升至200℃时,Hg⁰原子与单质Cu原子的吸附自由能从-22.47 kJ/mol下降至-13.96 kJ/mol,这些结果为深入了解Hg⁰在Cu(111)表面的反应机理提供了理论基础。     

Si表面吸附GaN的第一性原理研究

为了更好地了解Si表面对CaN的吸附,利用基于密度泛函理论的第一性原理平面波赝势方法,计算了Si(100)和Si(111)弛豫表面分别吸附GaN的电子结构、吸附能大小以及其态密度图.计算结果表明,相对于Si(111)表面,Si(100)表面更容易吸附GaN,在同等实验条件下,在Si(100)表面应更容易沉积GaN薄膜.采用ECR-MOPECVD工艺,于低温下在Si(100)衬底上沉积得到了GaN薄膜,XRD谱图表明该薄膜是一种晶体结构和无定形结构的混合结构.     

氧原子在Pt/Ni(111)合金表面扩散和次表面渗透的密度泛函理论研究

氧原子在Pt(111)/Ni(111)合金表面及其次表面的吸附、扩散和渗透是理解燃料电池阴极材料表面氧化的基础。研究人员采用基于密度泛函理论的第一性原理方法,研究了氧原子的吸附、扩散和渗透过程。结果表明:氧原子在纯金属表面更容易发生扩散,在Pt(111)-skin-Pt3Ni表面吸附后更容易跨越势垒向材料内部渗透。     

第一性原理方法探讨氮气在UO2(111)表面的吸附行为

采用第一性原理计算模拟方法对氮气分子及原子在UO2(111)表面的吸附行为进行了系统的研究。计算结果表明,N2在UO2(111)表面倾向于以分子吸附的形式存在,其最稳定的吸附构型为分子中心位于氧原子顶部或三重洞位的情形。两种构型下的N-N键的两端均指向相邻的另外两个高对称吸附位置。对于氮原子的表面吸附,发现其位于第二子层的铀原子的上方时最为稳定,吸附能为-4.792eV,为较强的化学吸附。而对次表面吸附的考察发现,氮原子嵌入最外氧原子层时的稳定性高于表面上吸附的情形。态密度分析表明,对于氮原子吸附,N 2p与U 5f电子态在费米能级附近有非常明显的轨道杂化,表明氮原子主要与铀原子发生了化学作用,N-U键存在共价成分。     

水冷壁镍涂层Na盐结渣的密度泛函理论研究

通过第一性原理(First principles)的密度泛函理论,利用Material studio的CASTEP模块,计算了不同覆盖度下Na盐在NiO涂层表面不同吸附位的吸附结构、吸附能、差分电荷密度及局域态密度,从原子层面研究通过铁基材料表面Ni涂层减轻结渣的机理。由表面吸附的分析可知,Na在涂层NiO(111)面的吸附稳定位为洞位;由差分电荷密度分析可知,涂层水冷壁表面发生的煤灰粘结过程主要是物理吸附过程;由洞位局域态密度分析可知,计算模型越接近实际模型,Na3s轨道和Ni3d轨道反键态电子越多,成键态电子越少,平均成键电子数越少,Na与Ni之间的相互作用越弱,导致吸附能数值减小,从而说明通过Ni涂层技术可以大大减轻Na盐结渣。     

Ge(111)表面氯自组装系统的近边X射线吸收精细结构理论研究

利用多重散射团簇方法 (MSC)首次对Cl/Ge(111)自组装系统的Cl原子K边X射线吸收精细结构 (NEXFAS)进行了详细的计算和分析。研究揭示了实验NEXFAS谱峰的物理起源。其中最显著一个峰来源于Cl和正位于其下的Ge之间的散射。同时还得到了吸附系统的局域结构 ;Cl吸附在Ge(111)面的顶位 ,吸附高度是 0 2 15± 0 0 0 5nm ,Cl在Ge(111)表面自组装形成了一个单分子层。这些结果和广延X射线吸收精细结构 (EXFAS)结论以及从头计算的结果相互吻合     

水热法制备二氧化铈纳米空心球及其吸附性能研究

用六水硝酸铈(Ce(NO_3)_3·6H_2O)作为铈源,以聚乙烯吡咯烷酮(PVP)为表面活性剂,在乙二醇的水溶液中通过水热法制备了单分散、粒径较均一的CeO_2纳米空心球。利用傅立叶转换红外分析(FT-IR)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、X射线能谱(XPS)、N_2等温吸附-解吸及紫外-可见光谱(UV-Vis)来表征CeO_2纳米空心球并研究其吸附性能。结果表明,水热法制备的CeO_2空心球是由立方萤石结构的纳米颗粒组装成的介孔中空材料,孔径分布窄,尺寸约为3~5 nm,空心球的直径约为400 nm,壁厚30 nm左右,空心球的BET比表面积为76.86 m2·g-1。讨论了CeO_2空心球的制备机理,所制备的CeO_2空心球对重铬酸钾溶液的吸附率可达到70%,约为CeO_2粉末的3倍。     

硝酸表面氧化改性木质活性碳纤维

采用2~14mol/L的硝酸,在23~83℃下,对木质活性碳纤维(WACF)浸渍氧化改性1~8h后,通过Raman、XPS、水吸附和汞吸附等表征表面官能团的结构性能。结果表明,硝酸氧化能力强,可以增加氧原子浓度。酚基、醇基、羟基、羧基官能团随着硝酸浓度增大而增多,酚基和醇基随着浸渍时间的延长而减少,羟基随着浸渍时间的延长而显著增多。WACF表面的石墨化程度随硝酸浓度增大而提高,芯部石墨化程度整体提高但不随浓度梯度的变化而变化。硝酸改性后WACF的水吸附孔容降低,水吸附比表面积显著增加。WACF对HgCl2的吸附量随着硝酸浓度的增大、温度的升高和浸渍时间的延长而增大。以WACF的吸附能力为研究目标,通过对其形貌、晶体结构、表面官能团等进行表征,揭示影响水吸附、汞吸附性能的表面结构特性和化学特性的内在规律,研究结果对WACF功能化利用有指导意义。     

HgCl_2-ZnCl_2-ScCl_3-CeCl_3/C低汞复合催化剂合成氯乙烯的催化机理

以氯化锌(ZnCl_2)、氯化钪(ScCl_3)和氯化铈(CeCl_3)为助催化剂,采用浸渍法制备氯乙烯(VCM)合成用低汞复合催化剂HgCl_2-ZnCl_2-ScCl_3-CeCl_3/C。研究了含稀土氯化物低汞复合催化剂在氯乙烯合成中的催化机理。结果表明,HgCl_2的催化机理遵循不对称合成反应立体选择性和立体专一性原则,按自由基和氢转移机理进行;稀土金属氯化物ScCl_3和CeCl_3与ZnCl_2和HgCl_2形成二维簇状螯合物,这增大了C2H2和HCl分子的活化百分数,提高了氯乙烯合成反应几率。     

Effects of chemical functional groups on elemental mercury adsorption on carbonaceous surfaces

A systematic theoretical study using density functional theory is performed to provide molecular-level understanding of the effects of chemical functional groups on mercury adsorption on carbonaceous surfaces. The zigzag and armchair edges were used in modeling the carbonaceous surfaces to simulate different adsorption sites. The edge atoms on the upper side of the models are unsaturated to simulate active sites. All calculations (optimizations, energies, and frequencies) were made at B3PW91 density functional theory level, using RCEP60VDZ basis set for mercury and 6-31G(d) pople basis set for other atoms. The results indicate that the embedding of halogen atom can increase the activity of its neighboring site which in turn increases the adsorption capacity of the carbonaceous surface for Hg(0). The adsorption belongs to chemisorptions, which is in good agreement with the experimental results. For the effects of oxygen functional groups, lactone, carbonyl and semiquinone favor Hg(0) adsorption because they increase the neighboring site's activity for mercury adsorption. On the contrary, phenol and carboxyl functional groups show a physisorption of Hg(0), and reduce Hg capture. This result can explain the seemingly conflicting experimental results reported in the literature concerning the influence of oxygen functional groups on mercury adsorption on carbonaceous surface.     

Immobilization of aqueous Hg(II) by mackinawite (FeS)

As one of the major constituents of acid volatile sulfide (AVS) in anoxic sediments, mackinawite (FeS) is known for its ability to scavenge trace metals. The interaction between aqueous Hg(II) (added as HgCl(2)) and synthetic FeS was studied via batch sorption experiments conducted under anaerobic conditions. Due to the release of H(+) during formation of hydrolyzed Hg(II) species which is more reactive than Hg(2+) in surface adsorption, the equilibrium pH decreased with the increase in Hg(II)/FeS molar ratio. Counteracting the loss of FeS solids at lower pH, the maximum capacity for FeS to remove aqueous Hg(II) was approximately 0.75 mol Hg(II) (mol FeS)(-1). The comparison of X-ray power diffraction (XRPD) patterns of synthetic FeS sorbent before and after sorption showed that the major products formed from the interaction between FeS and the aqueous Hg(II) were metacinnabar, cinnabar, and mercury iron sulfides. With the addition of FeS at 0.4 g L(-1) to a 1 mM Hg(II) solution with an initial pH of 5.6, Fe(2+) release was approximately 0.77 mol Fe(2+) per mol Hg(II) removed, suggesting that 77% of Hg(II) was removed via precipitation reaction under these conditions, with 23% of Hg(II) removed by adsorption. Aeration does not cause significant release of Hg(II) into the water phase.     

Mercury adsorption on granular activated carbon in aqueous solutions containing nitrates and chlorides

Adsorption is an effective process to remove mercury from polluted waters. In spite of the great number of experiments on this subject, the assessment of the optimal working conditions for industrial processes is suffering the lack of reliable models to describe the main adsorption mechanisms. This paper presents a critical analysis of mercury adsorption on an activated carbon, based on the use of chemical speciation analysis to find out correlations between mercury adsorption and concentration of dissolved species. To support this analysis, a comprehensive experimental study on mercury adsorption at different mercury concentrations, temperatures and pH was carried out in model aqueous solutions. This study pointed out that mercury capture occurs mainly through adsorption of cationic species, the adsorption of anions being significant only for basic pH. Furthermore, it was shown that HgOH(+) and Hg(2+) are captured to a higher extent than HgCl(+), but their adsorption is more sensitive to solution pH. Tests on the effect of temperature in a range from 10 to 55 °C showed a peculiar non-monotonic trend for mercury solution containing chlorides. The chemical speciation and the assumption of adsorption exothermicity allow describing this experimental finding without considering the occurrence of different adsorption mechanisms at different temperature.     

Adsorption and dissociation of the O2 on W(111) surface: a density functional theory study

The adsorption and dissociation of O2 molecules on W(111) surface have been studied at the density functional theory (DFT) level in conjunction with the projector augmented wave (PAW) method. All passable dissociation reaction paths of O2 molecule on W(111) surface are considered. The nudged elastic band (NEB) method is applied to locate transition states, and minimum energy pathways (MEP). We find that there is an existing of little barriers for the dissociations reaction of O2 molecule. Ab initio molecular dynamics simulation is also preformed to study the adsorption and dissociation mechanism of O2 molecules on the W(111) surface. Our results indicate that O2 molecule will be dissociated by inclined deposition at temperature of 10 K, but can stable adsorb on top site by normal deposition. The change of bond length and adsorption energy in process of dissociation of O2 molecules on the W(111) surface are also calculated. The O2 coverage effect is also discussed in this paper.     

Effect of morphology of dispersed nano-CeO2 on far infrared emission property of natural tourmaline

Dispersed nano-CeO2 successfully grew on the surface of natural tourmaline powders by a precipitation method. The results of Fourier transform infrared spectroscopy (FTIR) showed that CeO2 (111) nanospots could apparently enhance the far infrared emission property of tourmaline in relation to CeO2 nanoparticles. This is the first report regarding the effect of the morphology of nano-CeO2 on the far infrared emission property of natural tourmaline. The results of the characterization by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) showed that CeO2 (111) nanospots have much more chemisorbed oxygen than CeO2 nanoparticles, which is beneficial to the unit cell volume shrinkage of tourmaline, thus increasing its far infrared emissivity.     

Functionalized diatom silica microparticles for removal of mercury ions

Diatom silica microparticles were chemically modified with self-assembled monolayers of 3-mercaptopropyl-trimethoxysilane (MPTMS), 3-aminopropyl-trimethoxysilane (APTES) and n-(2-aminoethyl)-3-aminopropyl-trimethoxysilane (AEAPTMS), and their application for the adsorption of mercury ions (Hg(II)) is demonstrated. Fourier transform infrared spectroscopy and x-ray photoelectron spectroscopy analyses revealed that the functional groups (–SH or –NH₂) were successfully grafted onto the diatom silica surface. The kinetics and efficiency of Hg(II) adsorption were markedly improved by the chemical functionalization of diatom microparticles. The relationship among the type of functional groups, pH and adsorption efficiency of mercury ions was established. The Hg(II) adsorption reached equilibrium within 60 min with maximum adsorption capacities of 185.2, 131.7 and 169.5 mg g⁻¹ for particles functionalized with MPTMS, APTES and AEAPTMS, respectively. The adsorption behavior followed a pseudo-second-order reaction model and Langmuirian isotherm. These results show that mercapto- or amino-functionalized diatom microparticles are promising natural, cost-effective and environmentally benign adsorbents suitable for the removal of mercury ions from aqueous solutions.     

Functionalized diatom silica microparticles for removal of mercury ions

Abstract

Diatom silica microparticles were chemically modified with self-assembled monolayers of 3-mercaptopropyl-trimethoxysilane (MPTMS), 3-aminopropyl-trimethoxysilane (APTES) and n-(2-aminoethyl)-3-aminopropyl-trimethoxysilane (AEAPTMS), and their application for the adsorption of mercury ions (Hg(II)) is demonstrated. Fourier transform infrared spectroscopy and x-ray photoelectron spectroscopy analyses revealed that the functional groups (–SH or –NH₂) were successfully grafted onto the diatom silica surface. The kinetics and efficiency of Hg(II) adsorption were markedly improved by the chemical functionalization of diatom microparticles. The relationship among the type of functional groups, pH and adsorption efficiency of mercury ions was established. The Hg(II) adsorption reached equilibrium within 60 min with maximum adsorption capacities of 185.2, 131.7 and 169.5 mg g^?1 for particles functionalized with MPTMS, APTES and AEAPTMS, respectively. The adsorption behavior followed a pseudo-second-order reaction model and Langmuirian isotherm. These results show that mercapto- or amino-functionalized diatom microparticles are promising natural, cost-effective and environmentally benign adsorbents suitable for the removal of mercury ions from aqueous solutions.     

Use of biogenic and abiotic elemental selenium nanospheres to sequester elemental mercury released from mercury contaminated museum specimens

Mercuric chloride solutions have historically been used as pesticides to prevent bacterial, fungal and insect degradation of herbarium specimens. The University of Manchester museum herbarium contains over a million specimens from numerous collections, many preserved using HgCl(2) and its transformation to Hg(v)(0) represents a health risk to herbarium staff. Elevated mercury concentrations in work areas (～ 1.7 μg m(-3)) are below advised safe levels (<25 μg m(-3)) but up to 90 μg m(-3) mercury vapour was measured in specimen boxes, representing a risk when accessing the samples. Mercury vapour release correlated strongly with temperature. Mercury salts were observed on botanical specimens at concentrations up to 2.85 wt% (bulk); XPS, SEM-EDS and XANES suggest the presence of residual HgCl(2) as well as cubic HgS and HgO. Bacterially derived, amorphous nanospheres of elemental selenium effectively sequestered the mercury vapour in the specimen boxes (up to 19 wt%), and analysis demonstrated that the Hg(v)(0) was oxidised by the selenium to form stable HgSe on the surface of the nanospheres. Biogenic Se(0) can be used to reduce Hg(v)(0) in long term, slow release environments.     

Au(111)电极表面溴离子吸附诱导的表面应力的理论研究

以Br~-为例,应用格子气模型,建立了阴离子吸附层对Au(111)电极表面应力贡献的统计热力学理论,计算了吸附层Br~-间的相互作用能及表面应力的贡献.计算结果表明,总的表面应力是压缩性的;在高覆盖度区域,表面应力与覆盖度近似呈直线关系;在表面吸附层应力的多种物理起源中,通过底物的分子间作用力有着决定性的贡献,揭示了分子的吸附能间接地起着重要作用.