FTIR和XPS对沸石合成特性及Cr(Ⅲ)去除机制的谱学表征

以粉煤灰为原料,采用优化的水热晶化法合成沸石,使用XRD,SEM和ζ电位分析沸石产品的组成特性,借助FTIR和XPS等揭示废水中Cr(Ⅲ)的去除机制。合成产品主要为NaP1型沸石,在pH值8～12区间内,ζ电位由-8.72mV降到-24.46mV。准二级方程和Langmuir等温线对试验的拟合效果更好,理论饱和吸附量为33.557 0mg.g-1。FTIR图谱表明—OH和Si—O类官能团在反应过程中有重要贡献。XPS全谱发现:结合能576.45eV为Cr(2p3/2)的特征峰,揭示了吸附过程的有效性。吸附Cr(Ⅲ)后,沸石中Si—Si和Si—O对应的结合能增加了0.25和0.60eV,含Si官能团可能与Cr(Ⅲ)发生了配位反应。O(1s)的结合能在反应后变得更低。这些证据表明:沸石对Cr(Ⅲ)的去除过程是物理吸附和化学吸附共同作用的结果。     

低成本吸附剂稻壳灰对Cr(Ⅵ)去除机制的谱学表征

以低成本稻壳灰作为吸附剂,使用FTIR,SEM,XPS,XRD,XRF等分析手段,研究稻壳灰对Cr(Ⅵ)的去除机制。FTIR研究表明酰胺Ⅱ带,Si—O—Si,O—Si—O等在Cr(Ⅵ)去除过程中有一定贡献。由SEM图片清晰可见：吸附Cr(Ⅵ)后,稻壳灰表面分布有众多的光亮沉积物。XPS图谱证明：稻壳灰的主要组成元素为C,N,O,P和Si;C元素的存在状态以醛酮类为主,含C官能团与Cr(Ⅵ)发生了配位反应;N元素以—NH₂形态为主,Cr(Ⅵ)可能以静电作用与含N基团结合,并以物理吸附为主;Si的存在以Si—O为主,含Si官能团可能与Cr(Ⅵ)发生了配位反应。XRD分析结果表明：谱图中出现的峰是典型的SiO2特征峰;稻壳灰的结晶度增加,表明稻壳灰与Cr(Ⅵ)形成了具有晶体结构的金属化合物。XRF研究发现,K,Na,Mg和Ca的元素含量在吸附前后有所变化,另有两种新元素出现,这说明吸附过程存在离子交换机制。所有这些皆表明：各种官能团在Cr(Ⅵ)去除过程中的角色各不相同,无机微沉淀机制、氧化还原机制、表面络合机制、离子交换机制等是稻壳灰去除Cr(Ⅵ)的主要途径。这可以为吸附技术的实际应用提供理论支持。     

古交飞灰不同粒径颗粒的XRD及FTIR研究

我国每年产生大量的粉煤灰,不同粒径的粉煤灰在处置利用方面存在较大差异。为探究不同粒径粉煤灰物质组成及结构的差异,选取古交飞灰为研究对象,将其筛分成8个粒度级别,运用X射线衍射(XRD)及傅里叶变换红外光谱(FTIR)表征。结果表明:XRD图谱显示古交飞灰主要物质组成为非晶相玻璃体(61.93%～74.76%),莫来石(20.45%～29.59%)与少量石英(1.23%～5.64%)。随着粒径的增加,莫来石含量降低,石英含量先增加后降低,而玻璃体呈现整体上升的趋势。FTIR图谱显示Si—O(Si, Al)反对称伸缩振动峰为主要化学键(58.86%～67.39%),其次为Si—O—(Si)弯曲振动(15.28%～21.40%), Si—O—Si对称伸缩振动(6.18%～9.67%), Si—O—(Al)对称伸缩振动(0.79%～4.02%)。随着粒径的增加, Si—O(Si, Al)反对称伸缩振动相对增加, Si—O—(Si)弯曲振动降低,而Si—O—Si对称伸缩振动与Si—O—(Al)对称伸缩振动波有明显变化规律。FTIR中Si—O(Si, Al)反对称伸缩振动峰主要为飞灰中的玻璃体的吸收峰,其相对含量随着粒度的增加而增加与XRD定量所得玻璃体含量变化趋势整体一致。464 cm~(-1)附近石英的Si—O—(Si)弯曲振动, 1 090 cm~(-1)附近石英的Si—O—Si反对称伸缩振动相对含量的变化趋势与XRD定量所得石英百分含量的结果基本一致。不同粒飞灰中莫来石556 cm~(-1)处强吸收峰的相对含量(y)与XRD计算所得莫来石含量(x%)呈线性关系:y=0.396x-1.997,R~2=0.868。     

工作压强对硅掺杂辉光放电聚合物结构和性能的影响

采用辉光放电聚合技术,在不同工作压强条件下制备了掺硅的辉光放电聚合物(Si-GDP)薄膜.并采用傅里叶变换红外吸收光谱和X射线光电子能谱(XPS)对Si-GDP薄膜进行了表征,分析了压强变化对其内部结构及成分的影响.利用紫外—可见光谱对Si-GDP薄膜的光学带隙进行了分析.结果表明:Si-GDP薄膜中Si元素主要以Si—C,Si—H,Si—O,Si—CH₃的键合形式存在;随着工作压强的增大,薄膜中Si—C键相对含量先减小后增加;从Si-GDP薄膜的XPS分析可以发现,C—C与C C含 关键词： 硅掺杂辉光放电聚合物薄膜 工作压强 傅里叶变换红外吸收光谱 X射线光电子能谱     

SiC外延层表面化学态的研究

用高分辨X射线光电子能谱仪(XPS)和傅里叶变换红外(FTIR)光谱仪研究了SiC外延层表面的组分结构. XPS宽扫描谱,红外掠反射吸收谱及红外镜面反射谱的解析结果说明SiC外延层表面是由Si—O—Si和Si—CH₂—Si聚合体构成的非晶SiC_xO_y:H. SiC外延层表面的化学态结构为Si(CH₂)₄,SiO(CH₂)₃,SiO₂(CH₃)₂,SiO₃(CH₃),Si—Si,游离H₂O,缔合OH,Si—OH,O和O₂. 根据化学态结构和元素电负性确定了化学态的各原子芯电子束缚能顺序,并与XPS窄扫描谱拟合结果相对比,建立了化学态与其束缚能的对应关系,进而用Si(CH₂)₄的实际C 1s束缚能值进行校正,确定了各化学态的束缚能. 结果发现,除了SiC_xO_y(x=1,2,3,4,x+y=4)的Si 2p束缚能彼此不同外,其C 1s和O 1s彼此也不相同,其中SiO₂(CH₃)₂和SiO₃(CH₃)的C 1s束缚能与CH_m和C—O中C 1s的相近,对此从化学态结构,元素电负性和邻位效应进行了解释. 关键词： SiC 化学态 XPS FTIR     

PTCDA/P-Si光电探测器欧姆接触层的XPS测试分析

在光电探测器PTCDA/P-Si芯片的有机层表面,成功制作出了比接触电阻为4.5×10-5Ω·cm2的低阻欧姆接触层。利用X射线光电子能谱(XPS)对Al/Ni/ITO的欧姆接触层界面的电子状态进行了测试和分析。结果表明,ITO中的In3d及Sn3d各出现两个分裂能级的谱峰,它们是In和Sn原子处于氧化环境的结合能。Ni2p有两个谱峰Ni2p(1)及Ni2p(2),低结合能位置Ni2p(1)对应于Ni原子被X射线激发产生的谱峰,说明NiITO之间没有发生化学反应,Ni层阻止了Al层被氧化成Al2O3;高结合能Ni2p(2)谱峰说明已形成了Al3Ni冶金相,有利于低阻欧姆接触层的形成。     

ICP-OES分析低钙粉煤灰在NaOH溶液中离子浸出规律

低钙粉煤灰潜在的火山灰活性释放缓慢限制了其大规模利用,通过碱激发提高粉煤灰中Si4+,Al3+和Ca2+等离子浸出率对于加快低钙粉煤灰活性释放具有积极作用。采用电感耦合等离子体发射光谱、傅里叶变换红外光谱、X射线衍射和扫描电子显微镜分别测试和分析了5种浓度NaOH溶液对低钙粉煤灰激发过程中Si4+,Al3+和Ca2+的浸出规律、化学基团变化、水化产物生成及微观形貌演化。结果表明：碱激发作用显著提高了低钙粉煤灰中Si4+,Al3+和Ca2+浸出率,三种离子浸出率大小为：Si4+＞Al3+＞Ca2+,其中Si4+和Al3+浸出率随NaOH浓度增加而增加,随浸出时间延长呈对数规律升高;Ca2+由于在NaOH溶液中生成Ca(OH)₂沉淀,其浸出率大小表现为在水中高,在NaOH溶液中低。红外光谱清晰地表征出低钙粉煤灰受碱激发作用后化学基团在指纹区(波数1 300 cm-1以下)的变化,且随碱激发时间的延长和碱浓度的增加变化愈加明显。水化产物和微观形貌的结果显示出粉煤灰颗粒表面受到碱侵蚀发生解聚,在OH-催化下,硅铝单体分子重新排列形成硅酸盐和铝酸盐低聚络合物,通过亲核取代反应形成铝硅酸盐的低聚态溶胶,并进一步与碱金属阳离子通过配位键或静电键的作用缩聚形成水化凝胶类产物。采用ICP-OES测试粉煤灰中离子浸出率可作为评价粉煤灰火山灰活性的一种快速和准确的方法。     

GS-MBE生长的GaP/Si的XPS研究

利用X射线光电子能谱(XPS)深度剖析方法对气体源分子束外延(GS-MBE)生长的GaP/Si异质结构进行了详细的分析.其结果表明:(1)外延层内Ga、P光电子峰与GaP相相符,且组份分布均匀,为正化学比GaP.(2)在不同富PH₃流量条件下生长的样品,其表面富P量稍有不同,而GaP外延层内的测试结果相同.界面也未见有P的富集.(3)XPS剖析至GaP/Si界面附近,随外延层界面向衬底过渡,Si2p光电子峰向高结合能方向移动,且其结合能高于原衬底p型Si,接近于n型Si.但Ga、P光电子峰未发现有明显能移.(4)在XPS检测限内,外延层内和界面都未见有C、O等沾污.这一研究表明:无污染的本底超高真空、相对过剩的富₃生长环境、成功的Si衬底清洗方法等措施保证了GS-MBE生长出正化学比GaP/Si外延异质结构.     

硅镁凝胶对杉木的强化及固着机制研究

硅镁凝胶浸渍改性杉木在物理力学性能方面提升较佳,探究硅镁凝胶在杉木中的固着性能和机制,对后续研究与创新具有一定意义。以硅镁凝胶为改性药剂,人工林杉木为基材,浸渍干燥后制得改性杉木。通过FTIR和XPS分析杉木素材和改性杉木的化学成分和结合方式,并对硅镁凝胶在木材中的分布以及改性杉木的渗透性进行探讨。实验结果表明：硅镁凝胶浸渍改性杉木的物理力学性能得到明显改善,密度均达到0.5 g·cm-3以上,抗压强度和抗弯强度相比杉木素材分别提升了99.73%和58.48%,端面硬度从3 659 N提升到5 843 N,基本已达到中等木材的性能指标。EDS结果证明药剂在杉木细胞腔中填充状况良好,Si,O,Na和Mg等主要元素与浸渍药剂硅镁凝胶相符且分布均匀。对浸洗前后的改性杉木试样和素材分别进行分层XPS测试,改性材的O/C增大,各元素在不同深度的含量十分接近,硅镁凝胶在杉木中分布均匀,具有良好的渗透性;浸洗后Si元素含量稳定,而钠元素有所降低,可能是部分钠盐的溶解流失造成,且不同深度的元素含量变化趋于一致,改性杉木的抗流失性较好。相比于硅酸钠浸渍改性杉木,硅镁凝胶改性杉木在96 h流失率降低到10.8%,抗流失效果较好。FTIR测试结果表明硅酸钠溶液对杉木的木质素和半纤维素有破坏和脱出作用,对杉木的通透性有所改善,且更容易与药剂形成化学键结合。C,O和Si元素的XPS谱图结果表明,改性后C(1s)向低结合能偏移,性质更加稳定,O—H结合大量减少,Si—O结合增多,硅镁凝胶能够在杉木中形成稳定的Si—O—C化学结构,药剂能够在细胞壁上实现高效固着。研究结果为改性材的药剂流失性检测和固着性研究提供新的思路,为硅镁凝胶浸渍改性杉木后续研究提供一定的理论支持。     

红外光谱、 XPS分析比较Ca~(2+),Fe~(3+)对石英的活化机理

铁精矿浮选脱硅过程中,矿浆中的难免阳离子(Ca~(2+), Fe~(3+))对阴离子捕收石英的可浮性有重要影响,而搞清难免阳离子对含石英等脉石矿物的活化机制,对解决超纯铁精矿脱硅技术难题有重要意义。目前关于捕收剂对石英吸附结构的研究较多,而难免离子活化石英的吸附结构及吸附强弱发生机制研究较少。因此,采用红外光谱、 XPS检测手段对难免离子(Ca~(2+), Fe~(3+))活化石英浮选进行光谱学表征,同时解析石英中含氧官能团及难免离子的赋存形式,分析其活化机理。红外检测结果表明,在适宜的pH值条件下, Ca~(2+)和Fe~(3+)的加入,对SDS捕收剂浮选石英均有活化作用,而活化后的石英与SDS作用,其间既包括物理吸附,也包括化学吸附;而且Fe~(3+)活化作用下的Si—O特征峰红移波数大于Ca~(2+)活化作用下的红移波数,是由于Ca~(2+)活化石英是单氧-硅键作用,其键能小,吸附弱,而Fe~(3+)活化石英是双氧-硅键作用,其键能大,吸附强。XPS测试表明, Fe~(3+)活化石英的结合能(Fe(2p)结合能为711.16 eV)强于Ca~(2+)活化石英的结合能(Ca(2p)结合能为346.93 eV),其Si(2s)和Si(2p)结合能化学位移量更大,说明Fe~(3+)活化作用下其化学吸附更稳定、更致密,且产生两个活性位点,在石英表面生成稳定的Fe基六元环螯合物;而对比Fe~(3+)和Ca~(2+)活化作用下的化学吸附不稳定、不致密,在石英表面生成Ca基链状络合物。综合红外光谱、 XPS分析表明, Fe~(3+)比Ca~(2+)有更强的活化作用,同时加强了药剂与石英表面的化学吸附和物理吸附,更利于活化石英的浮选。     

Characterization of Cr/SiO2 catalysts and ethylene polymerization by XPS

Cr/SiO₂ catalysts with 1 or 3 wt.% Cr loadings and different chromium precursors were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). A method to determine chromium species in the sample was developed through the decomposition of the Cr 2p XPS spectrum in Cr⁶⁺ and Cr³⁺ standard spectra. The results of the binding energy from the Cr 2p region and of the distribution of chromium species allowed to evaluate the dynamic photo-reduction of the surface chromium species during XPS analysis. Photo-reduction of surface Cr⁶⁺ to Cr³⁺ species was verified for all samples supported in silica, depending on the precursor and chromium content. Bulk CrO₃ and Cr₂O₃ standards did not reveal variation in the binding energy of Cr 2p_3/2, but a physical mixture of CrO₃ with SiO₂ presented photo-reduction. The behavior of this mixture resembled to the catalysts and suggests the participation of the surface hydroxyls of silica in the photo-reduction process. XPS intensity measurements for assessing dispersion of chromium oxide were used to compare the calcined and reduced catalysts to different chromium precursors. Polyethylene chains were detected by in situ XPS, while oligomerization products were not observed.     

用XPS研究高灰熔融温度煤灰的矿物结构转化

高灰熔点X煤通过添加钙镁复配(W_CaO/W_MgO=1)助熔剂降低灰熔点,在模拟煤气化过程中制备灰渣,用X射线光电子能谱(XPS)分析不同温度点灰渣中O,Si,Al,Ca,Mg的存在形态及演化过程。认为钙镁复配助熔剂降低灰熔点主要是作用在硅、铝、氧结构变化上,表现为铝元素结构中铝氧配位方式的变化,即四配位的铝氧四面体[AlO₄]和六配位的铝氧八面体[AlO₆]随温度的变化而变化;硅元素结构中SiO₂链的破坏,Ca2+和Mg2+加入会破坏SiO₂链,使得桥氧硅变为非桥氧硅;以及氧元素结构中桥氧键断裂和非桥氧键形成。结合Factsage热力学分析软件,分析了添加钙镁复配助熔剂后,煤灰渣的高温相平衡组成,从矿物的结构变化研究助熔剂的助熔机理。结果表明,添加钙镁复配助熔剂后,Ca2+和Mg2+易与硅氧和铝氧四面体以及铝氧八面体中非桥氧键结合,生成低熔点的长石类矿物和镁质矿物,从而降低煤灰熔融温度。     

Bias voltage effect on the structure and property of chromium copper-diamond-like carbon multilayer films fabricated by cathodic arc plasma

Chromium copper-diamond-like carbon (Cr:Cu)-DLC films were deposited onto silicon and by cathodic arc evaporation process using chromium (Cr) and copper (Cu) target arc sources to provide Cr and Cu in the Me-DLC. Acetylene reactive gases were the carbon source and activated at 180 °C at 13 mTorr, and a substrate bias voltage was varied from −50 V to −200 V to provide the (Cr:Cu)-DLC structure. The structure, interface, and chemical bonding state of the produced film were analyzed by transmission electron microscope (TEM), IR Fourier transform (FTIR) spectra, and X-ray photoelectron spectroscopy (XPS). The results showed that the Cr-containing a-C:H/Cu coatings exhibited an amorphous layer of DLC:Cr layer and a crystalline layer of Cu multilayer structure. The profiles of sp³/sp² (XPS) ratios corresponded to the change of microhardness profile by varying the pressure of the negative DC bias voltage. These (Cr:Cu)-DLC coatings are promising materials for soft substrate protective coatings.     

FTIR和XPS对含低价Cr混合物物相分析的应用研究

因Cr的可变价态较多,且在制备低价Cr氧化物过程中,经常出现不同价态的中间体过渡产物,这些过渡产物的性质各异,往往对最终产物的形貌特征产生显著影响。以KCrO₂为原料制备低价Cr化合物的过程中出现了组成比较复杂的中间产物,为探讨反应机理并优化工艺流程,文章结合光电子能谱(XPS),傅里叶变换红外光谱(FTIR),X射线衍射(XRD),电感耦合等离子发射光谱(ICP-AES)元素分析和化学滴定分析对KCrO₂的还原中间产物进行了物相分析。XPS能谱分析表明, 还原中间产物中Cr元素是以三价形态存在的;对不同还原温度所得的中间产物的FTIR与其他方法所得的水合氧化Cr的FTIR进行比较, 并结合XRD测试,元素分析,化学分析结果可以得出下面结论：中间产物主要组成为Cr(OH)₃·nH₂O,CrOOH。还有少量的KOH或KCrO₂。在对中间物相分析的基础上, 对还原过程可能发生的反应进行了推测。     

城市下水污泥和煤/LPG在循环流化床上的混烧试验研究

在高6000 mm、直径300mm的循环流化床上进行了含水率为79％的湿污泥与煤／石油液化气(LPG)的混烧试验。试验结果表明:无论用煤还是LPG作为辅助燃料,试验都能在设定的工况条件下稳定运行;向炉内加入石灰石的量达到钙硫摩尔比为3．4∶1时,二氧化硫和氯化氢的排放达标,脱硫效率和脱氯效率分别为75％和94％;在试验中, 烟气中NOx排放、烟气中汞含量和二恶英类排放都不超标;试验产生的飞灰含碳量低,飞灰中痕量元素的浸出毒性不超标;计算表明,如果利用余热干燥污泥和预热空气可有效地减少辅助燃料的消耗量。     

Spectroscopic characterization analysis on Cr (VI) removal mechanism by low-cost adsorbent of rice husk ash

Analyzing methods of Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction analysis (XRD) and X-ray fluorescence spectroscopy (XRF) were used to reveal the adsorption mechanism of Cr(VI) by low-cost adsorbent of rice husk ash. Results of FTIR showed that amide II band, Si--O--Si, and (O--Si--O were important for Cr(VI) removal. SEM micrographs suggested that series of needle-shaped precipitation appeared on cell surface, and inorganic precipitation mechanism and redox mechanism might work in the test. XPS spectra showed that main elements of rice husk ash were C, N, O, P and Si, existing state of C was mainly aldoketones groups, coordi nation reaction existed between C functional groups and Cr(VI); N element, --NH2 in chief, could remove Cr(VI) in the way of physical adsorption based on electrostatic interaction; Si--O might be useful in adsorption process. XRD data suggested representative characteristic adsorption band of SiO2, and the increasing crystallinity of rice husk ash showed metallic compound formed between Cr(VI) and rice husk ash. XRF results indicated that the content of K, Na, Mg and Ca changed, and two new elements were detected, the evidence of ion exchange mechanism. The functional groups played different roles in Cr(VI) adsorption process, and inorganic precipitation mechanism, redox mechanism, surf-complexation mechanism and ion exchange mechanism were important ways in Cr(VI) removal, which could provide theoretical support in further application.     

An investigation of the effect of ultrasonic waves on the efficiency of silicon extraction from coal fly ash

Burning of coal accounts for an enormous proportion of the current energy supply, especially in developing countries. Burning of coal produces large amounts of coal fly ash, which causes serious environmental problems unless it is managed properly. Using chemical analysis, we found that coal fly ash could be a promising source of Si, Al, Ca and some rare earth elements, especially with the assistance of some measures such as ultrasound. In this study, we extracted silicon from coal fly ash using an alkaline dissolution strategy and investigated the effects of temperature and ultrasonic power on the efficiency of silicon extraction. During a 70 min reaction, the efficiency of silicon extraction increased markedly, from 9.41% to 34.96%, as the reaction temperature increased from 70 °C to 110 °C. With ultrasound assistance, ultrasonic waves enhanced the extraction of silicon at both 80 °C and 110 °C at 720 W ultrasound, increasing the efficiency of silicon extraction from 6.01% to 15.36% and from 34.96% to 54.42%, respectively. However, at 900 W ultrasonic power, extraction was slightly inhibited at both temperatures, causing a little decrease in efficiency.     

Thermodynamic and statistical studies of supersaturated ternary solutions

The influence of chromium ions Cr3+ on properties of supersaturated aqueous solution of ammonium sulfate (NH4)2SO4 has been studied employing containerless electrodynamic levitation of single microdroplets of this solution with known concentration of Cr3+ ions. The water activity versus solute concentration was measured in three different sets of experiments corresponding to different initial concentrations of Cr3+ ions. Theoretical treatment of the experimental results obtained is developed employing the theory of supersaturated electrolyte solutions [Phys. Rev. E 52, 1325 (1995)]. This treatment has allowed the following two conclusions. First, spinodal concentration is a decreasing function of Cr3+ concentration. Second, solute clusters formed in the presence of Cr3+ ions demonstrate complex behavior with respect to binding water molecules: (a) at low and moderate supersaturations, they bind more water molecules than clusters formed in the absence of an impurity; and (b) at high supersaturations, they bind less water molecules than clusters formed in the absence of an impurity.