乳酸杆菌A09吸附还原Ag（Ⅰ）的谱学表征

Pooley[1]发现氧化亚铁硫杆菌(Thiobacillusferroxidans)和氧化硫硫杆菌(Thiobacillusthiooxidans)能在其细胞表面累积银,形成Ag2S,每克干重细胞吸附250mgAg2S.文献[2]也报导了类似的研究结果.一些霉菌也具有吸收金、银等重金属的能力[3].Brierley等[4]研究了用微生物制备回收贵金属的去除剂(MRA),用它能从摄影废液中回收银,每克MRA累积94mgAg;同时指出,贵金属生物吸附也包含金属离子被还原为金属的过程.在微生物吸附还原贵金属前期研究[5－9]的基础上,我们从金、银矿土等不同来源的细菌菌株中,筛选获得一株吸附、还原Ag＋…     

乳酸杆菌A09吸附还原Ag(I)的谱学表征

Pooley[1]发现氧化亚铁硫杆菌(Thiobacillus ferroxidans)和氧化硫硫杆菌(Thiobacillus thiooxidans)能在其细胞表面累积银,形成Ag2S,每克干重细胞吸附250 mg Ag2S.文献[2]也报导了类似的研究结果.一些霉菌也具有吸收金、银等重金属的能力[3].Brierley等[4]研究了用微生物制备回收贵金属的去除剂(MRA),用它能从摄影废液中回收银,每克MRA累积94 mg Ag;同时指出,贵金属生物吸附也包含金属离子被还原为金属的过程.     

贵金属离子非酶法生物还原机理初探

在微生物湿法冶金回收贵金属的研究工作中,掌握金属非酶法生物还原的作用过程及本质是优化浸出工艺条件,设计高效,经济的生物加收技术的关键,因此有关细菌固定金属的作用机制的研究一直为人们所关注,冻干的海藻（Chlorella vulgaris)和四氯金（Ⅲ）酸盐[AuCl4]-相互作用,Au3＋快速被还原为Au ,继而缓慢地被还原成Au[1],厌氧的脱硫弧菌属（Desulfovibrio desulfuricans)的休止细胞能将溶液中的钯离子还原为金属钯,用丙酮酸钠,甲酸钠或氢气作为电子供体[2],我们试图从失活细菌与金属离子的界面出发,利用谱学技术,考察细菌与金属离子之间的相互作用本质,为开发利用生物体作为吸附剂进行废水处理,回收贵重或有害金属以及制备高分散度负载型金属催化剂[3]提供理论依据。     

Pt,Ru和Pd助剂对F-T合成中Co/γ-Al2O3催化剂性能的影响

 采用浸渍法制备了添加贵金属Pt,Ru和Pd助剂的Co/γ-Al2O3催化剂,并考察了它们在F-T合成反应中的催化性能. 结果表明,添加贵金属助剂可以显著提高Co/γ-Al2O3催化剂的催化活性. XRD和TPR表征结果表明,贵金属助剂不但可以使催化剂的金属分散度增加,而且可以通过氢溢流促进催化剂表面活性相的Co3O4以及与载体Al2O3有相互作用的非活性相钴氧化物物种的还原,从而改善催化剂的还原性能. TPSR结果进一步表明,添加贵金属助剂后催化剂对CO的吸附解离能力增强,从而使吸附态CO的加氢活性提高.     

活性碳纤维对银离子还原吸附能力的改进

活性碳纤维不仅对有机物有高的吸附容量,对贵金属离子也具有强的还原吸附能力,可将Pd(Ⅱ）,Ag（Ⅰ）,Au（Ⅲ）等离子还原为金属单质。因而可用于提取矿液或加收废液中的贵金属。由此,提高或改善贵金属在活性碳纤维上的还原吸附容量或分布形成,显得非常重要。本文研究了活性碳纤维制备条件、表面氧化改性、以有负载有机物等对活性碳纤维还原能力的影响。结果表明,（1）制备条件对剑麻基活性碳纤维的还原能力有很大的影响。用H3PO4或ZnCl2活化的活性碳纤维对银离子具有更高的还原吸附容量,分别可达250和700mg/g,约为水蒸汽活化剑麻基活性碳纤维对银离子还原吸附容量的2倍和5倍。（2）过氧化氢、高锰酸钾、或硝酸等无机氧化剂对活性碳纤维进行表面改性,也能提高活性碳纤维的还原能力。结果表明,虽然改性活性碳纤维的比表面积和孔体积下降10-20%左右,但基表面含氧量及含氧基团的种类发生了改变。这些改性活性碳纤维对Ag(NH3)2^ 的还原吸附量大幅度提高,可达550mg/g以上。推断表面改性在活性碳纤维表面创造了更多有利于碱性条件下发生氧化还原的活性点。（3）在活性碳纤维表面负载适当的有机物如亚甲基蓝、苯胺或对硝基苯酚,也能显著提高活性碳纤维对Ag(NH3)2^ 的还原吸附能力。     

制备方法和助剂对贵金属铱催化剂还原性质的影响

通过应用TPR等方法研究了制备方法、焙烧温度和助剂氧化铈含量等对催化剂还原性质、吸附性能的影响 .结果表明分步浸渍法制备的催化剂活性中心比一步共浸渍法制备的催化剂的活性中心数量多 ;助剂氧化铈含量变化的催化剂中Ce含量为 1%时 ,催化剂的活性中心最多 ;共浸渍的催化剂中 ,加入助剂镁以后 ,使金属易于还原 ,加入助剂铈后 ,使贵金属难于还原     

N-羧甲基壳聚糖的制备及其对重金属离子吸附研究

采用氯乙酸和壳聚糖为原料制备了N-羧甲基壳聚糖,并研究了其对重金属离子Pb2+、Co2+、Ni2+、Cd2+的吸附行为。采用了XRD、FT-IR、1H-NMR对N-羧甲基壳聚糖进行了表征,对N-羧甲基壳聚糖的4种金属离子配合物进行了FT-IR表征。结果表明,N-羧甲基壳聚糖对Pb2+、Co2+、Ni2+、Cd2+的吸附能力优于壳聚糖,分子中羧基是主要的螯合基团。     

偕胺肟基纤维对铜(II)的吸附动力学

对含丙烯腈结构单元的高分子材料进行 CN的改性反应,偕胺肟化后的高分子材料可作为吸附剂,用于对水溶液中的金属离子吸附去除[1 4],也可用于稀土等贵金属的富集和回收[5 6]。作者以聚丙烯腈纤维改性所得偕胺肟纤维为吸附剂,对水溶液中的Cu2+进行吸附研究,着重研究了偕胺肟纤维对Cu2+的吸附反应动力学特征。1　实验部分1 1　主要试剂与仪器偕胺肟纤维按文献[7]方法制备,Cu2+溶液由硫酸铜(AR)和蒸馏水配制,其余试剂均为分析纯。WXF 120原子吸收分光光度计(北京瑞利分析有限公司),PXD 12数字式离子计(江苏电分析仪器厂),FC 104电子天…     

液膜分离富集金与测定微量金

提出采用乳状液膜体系分离、富集金。该体系包括协同流动载体（TBP和PMBP），表面活性剂（SPAN80），膜的增强剂（液体石蜡），膜溶剂（煤油）和内相（1％质量分数的NaOH水溶液）。实验结果表明，金的迁移率达90．5％以上。此条件下，许多共存金属高于如∑RE3+、Ag2+、Pd2+、Pt4+、Rh3+、Cu2+、Fe3+、Al3+、Pb2+、Zn2+、Mo6+、W6+、Mn2+、Sn4+、Te4+、Se4+、Ca2+和Mg2+等不被迁移，只有金能与这些金属离子得到满意的分离。该法已应用于测定提金溶液和氰化物没出贵金属溶液中的微量金，相对标准偏差为1．3％－3．9％。     

金属离子的光催化去除研究进展

利用光催化剂表面的光生电子或空穴等活性物种，通过还原或氧化反应去除水相中的金属离子，是与环境保护、贵金属回收或金属担载催化剂制备相关的重要过程。笔者结合半导体的结构特征，综述了利用光催化还原反应或氧化反应，对铬、汞、铜、镍、银及铂、钯等贵金属和锰、铀等的光催化去除效果，介绍了该技术在处理金属离子混合体系实现金属分离过程的应用。结合有关实验数据，对一些可能反应机制进行了探讨。对与环境保护及其它相关工艺过程的应用进行了介绍。     

冠醚聚合物的研究 Ⅱ.以聚硫醚为主链的硫杂冠醚聚合物的合成及其络合性能

本文报道了一种合成硫杂冠醚聚合物的新方法。以聚(2′-氯乙基-2,3-环硫丙基醚)为预聚物与二巯基化合物通过大分子反应直接环化,一步法合成了四种以聚硫醚为主链的新型硫杂冠醚聚合物(PD1-PD4)。并测定了它们对Ag~+、Au~(3+)、Pd~(2+)、Pt~(4+)、Cu~(2+)、Hg~(2+)、Zn~(2+)、Cd~(2+)、Pb~(2+)、Mg~(2+)、K~+、Ns~+等金属离子的络合性能。结果表明:它们除不络合K~+、Na~+、Mg~(2+)、Pb~(2+)外,对其它八种离子有不同程度的络合,其中对Ag~+、Au~(3+)、Pd~(2+)等贵金属离子的络合容量较高。     

螯合树脂研究——Ⅴ.巯基胺型螯合树脂的合成其吸附性能

本工作探索了一种合成巯基胺型螯合树脂的新方法.用环硫氯丙烷与多乙烯多胺作用只经一步反应,即可制得交联型巯基胺树脂,树脂中的配位原子氮和硫的含量较高,对贵金属离子金、银、钯具有良好的吸附性能.     

螯合树脂研究——Ⅷ.以聚硫醚为主链的氧杂多乙烯多胺型螯合树脂的合成及其吸附性能

由聚[2′-氯乙基-2,3-环硫丙基醚]和多乙烯声胺反应,合成了四种以聚硫醚为主链的氧杂多乙烯多胺型螯合树脂,它们对贵金属离子Au(Ⅲ)、Pd(Ⅱ)、Pt(Ⅳ)、Ag~+等具有优良的吸附性能。     

Sulfonated poly(ether ether ketone)/poly(vinyl alcohol) sensitizing system for solution photogeneration of small Ag, Au, and Cu crystallites

Illumination of air-free aqueous solutions containing sulfonated poly(ether ether ketone) and poly(vinyl alcohol) with 350 nm light results in benzophenone ketyl radicals of the polyketone. The polymer radicals form with a quantum yield 0.02 and decay with a second-order rate constant 6 orders of magnitude lower than that of typical alpha-hydroxy radicals. Evidence is presented that the polymeric benzophenone ketyl radicals reduce Ag+, Cu2+, and AuCl4- to metal particles of nanometer dimensions. Decreases in the reduction rates with increasing Ag(I), Cu(II), and Au(III) concentrations are explained using a kinetic model in which the metal ions quench the excited state of the polymeric benzophenone groups, which forms the macromolecular radicals. Quenching is fastest for Ag+, whereas Cu2+ and AuCl4- exhibit similar rate constants. Particle formation becomes more complex as the number of equivalents needed to reduce the metal ions increases; the Au(III) system is an extreme case where the radical reactions operate in parallel with secondary light-initiated and thermal reduction channels. For each metal ion, the polymer-initiated photoreactions produce crystallites possessing distinct properties, such as a very strong plasmon in the Ag case or the narrow size distribution exhibited by Au particles.     

Deposition of gold nanoparticles on silica spheres by electroless metal plating technique

A previously proposed method for metal deposition with silver [Kobayashi et al., Chem. Mater. 13 (2001) 1630] was extended to uniform deposition of gold nanoparticles on submicrometer-sized silica spheres. The present method consisted of three steps: (1) the adsorption of Sn(2+) ions took place on surface of silica particles, (2) Ag(+) ions added were reduced and simultaneously adsorbed to the surface, while Sn(2+) was oxidized to Sn(4+), and (3) Au(+) ions added were reduced and deposited on the Ag surface. TEM observation, X-ray diffractometry, and UV-vis absorption spectroscopy revealed that gold metal nanoparticles with an average particle size of 13 nm and a crystal size of 5.1 nm were formed on the silica spheres with a size of 273 nm at an Au concentration of 0.77 M.     

Removal of residual metal catalysts with iron/iron oxide nanoparticles from coordinating environments

The application of Fe@FexOy nanoparticles was examined for the sequestration of catalytic metal impurities from organic reaction products. An X-ray photoelectron spectroscopy (XPS) study of the recovered particles confirmed Fe@FexOy sequestered Co2+, Cu2+, Ni2+, RhX+, Pd2+, Ag+, and Pt4+ by coordination of the metal ion to the iron oxide surfaces and followed by subsequent reduction of the surface-bonded ions to their metallic state. Fe@FexOy metal sequestration was found to be effective for catalyst impurities in the absence of strongly coordinating environments but was inhibited by the presence of phosphines. Sequestration of phosphine-coordinated metal impurities was achieved through the addition of either cysteamine or 3-mercaptopropionic acid to the Fe@FexOy during sequestration. This approach was applied to model syntheses using Grubbs' Catalyst (first generation), Pd(PPh3)4, Pd2(dba)3, and Wilkinson's Catalyst (RhCl(PPh3)3).     

Density functional theory-based prediction of some aqueous-phase chemistry of superheavy element 111. Roentgenium(I) is the "softest" metal ion

A previous approach (Hancock, R. D.; Bartolotti, L. J. Inorg. Chem. 2005, 44, 7175) using DFT calculations to predict log K1 (formation constant) values for complexes of NH3 in aqueous solution was used to examine the solution chemistry of Rg(I) (element 111), which is a congener of Cu(I), Ag(I), and Au(I) in Group 1B. Rg(I) has as its most stable presently known isotope a t(1/2) of 3.6 s, so that its solution chemistry is not easily accessible. LFER (Linear free energy relationships) were established between DeltaE(g) calculated by DFT for the formation of monoamine complexes from the aquo ions in the gas phase, and DeltaG(aq) for the formation of the corresponding complexes in aqueous solution. For M2+, M3+, and M4+ ions, the gas-phase reaction was [M(H2O)6]n+(g) + NH3(g) = [M(H2O)5NH3]n+(g) + H2O(g) (1), while for M+ ions, the reaction was [M(H2O)2]+(g) + NH3(g) = [M(H2O)NH3]+(g) + H2O(g) (2). A value for DeltaG(aq) and for DeltaE for the formation of M = Cu2+ in reaction 1, not obtained previously, was calculated by DFT and shown to correlate well with the LFER obtained previously for other M2+ ions, supporting the LFER approach used here. The simpler use of DeltaE values instead of DeltaG(aq) values calculated by DFT for formation of monoamine complexes in the gas phase leads to LFER as good as the DeltaG-based correlations. Values of DeltaE were calculated by DFT to construct LFER with M+ = H+, and the Group 1B metal ions Cu+, Ag+, Au+, and Rg+, and with L = NH3, H2S, and PH3 in reaction 3: [M(H2O)2]+(g) + L(g) = [M(H2O)L]+g) + H2O(g) (3). Correlations involving DeltaE calculated by DMol3 for H+, Cu+, Ag+, and Au+ could reliably be used to construct LFER and estimate unknown log K1 values for Rg(I) complexes of NH3, PH3, and H2S calculated using the ADF (Amsterdam Density Functional) code. Log K1 values for Rg(I) complexes are predicted that suggest the Rg(I) ion to be a very strong Lewis acid that is extremely "soft" in the Pearson hard and soft acids and bases sense.     

Density functional theory-based prediction of the formation constants of complexes of ammonia in aqueous solution: indications of the role of relativistic effects in the solution chemistry of gold(I)

A prediction of the formation constants (log K1) for complexes of metal ions with a single NH3 ligand in aqueous solution, using quantum mechanical calculations, is reported. DeltaG values at 298 K in the gas phase for eq 1 (DeltaG(DFT)) were calculated for 34 metal ions using density functional theory (DFT), with the expectation that these would correlate with the free energy of complex formation in aqueous solution (DeltaG(aq)). [M(H2O)6]n+(g) + NH(3)(g) = [M(H2O)5NH3]n+(g) + H2O(g) (eq 1). The DeltaG(aq) values include the effects of complex changes in solvation on complex formation, which are not included in eq 1. It was anticipated that such changes in solvation would be constant or vary systematically with changes in the log K(1) value for different metal ions; therefore, simple correlations between DeltaG(DFT) and DeltaG(aq) were sought. The bulk of the log K1(NH3) values used to calculate DeltaG(aq) were not experimental, but estimated previously (Hancock 1978, 1980) from a variety of empirical correlations. Separate linear correlations between DeltaG(DFT) and DeltaG(aq) for metal ions of different charges (M2+, M3+, and M4+) were found. In plots of DeltaG(DFT) versus DeltaG(aq), the slopes ranged from 2.201 for M2+ ions down to 1.076 for M4+ ions, with intercepts increasing from M2+ to M4+ ions. Two separate correlations occurred for the M3+ ions, which appeared to correspond to small metal ions with a coordination number (CN) of 6 and to large metal ions with a higher CN in the vicinity of 7-9. The good correlation coefficients (R) in the range of 0.97-0.99 for all these separate correlations suggest that the approach used here may be the basis for future predictions of aqueous phase chemistry that would otherwise be experimentally inaccessible. Thus, the log K1(NH3) value for the transuranic Lr3+, which has a half-life of 3.6 h in its most stable isotope, is predicted to be 1.46. These calculations should also lead to a greater insight into the factors governing complex formation in aqueous solution. All of the above DFT calculations involved corrections for scalar relativistic effects (RE). Au has been described (Koltsoyannis 1997) as a "relativistic element". The chief effect of RE for group 11 ions is to favor linear coordination geometry and greatly increase covalence in the M-L bond. The correlation for M+ ions (H+, Cu+, Ag+, Au+) involved the preferred linear coordination of the [M(H2O)2]+ complexes, so that the DFT calculations of DeltaG for the gas-phase reaction in eq 2 were carried out for M = H+, Cu+, Ag+, and Au+. [M(H2O)2]+(g) + NH3(g) = [M(H2O)NH3]+(g) + H2O(g) (eq 2). Additional DFT calculations for eq 2 were carried out omitting corrections for RE. These indicated, in the absence of RE, virtually no change in the log K1(NH3) value for H+, a small decrease for Cu+, and a larger decrease for Ag+. There would, however, be a very large decrease in the log K1(NH3) value for Au(I) from 9.8 (RE included) to 1.6 (RE omitted). These results suggest that much of "soft" acid behavior in aqueous solution in the hard and soft acid-base classification of Pearson may be the result of RE in the elements close to Au in the periodic table.     

Synthesis and characterisation of morin-functionalised silica gel for the enrichment of some precious metal ions

Silica gel was firstly functionalised with aminopropyltrimethoxysilane obtaining the aminopropylsilica gel (APSG). The APSG was reacted subsequently with morin yielding morin-bonded silica gel (morin-APSG). The structure was investigated and confirmed by elemental and thermogravimetric analyses, IR and (13)C NMR spectral studies. Morin-APSG was found to be highly stable in common organic solvents, acidic medium (<2molL(-1) HCl, HNO(3)) or alkaline medium up to pH 8. The separation and preconcentration of Ag(I), Au(III), Pd(II), Pt(II) and Rh(III) from aqueous medium using morin-APSG was studied. The optimum pH values for the separation of Ag(I), Au(III), Pd(II), Pt(II) and Rh(III) on the sorbent are 5.7, 2.2, 3.7, 3.7 and 6.8, giving rise to separation efficiencies of 43.9, 85.9, 97.7, 60.9 and 91.0%, respectively, where the activity was found to be >90% in the presence of acetate ion. The ion sorption capacity of morin-APSG towards Cu(II) at pH 5.5 was found to be 0.249mmolg(-1) where the sorption capacities of Ag(I) and Pd(II) were 0.087 and 0.121mmolg(-1) and 0.222 and 0.241mmolg(-1) at pH 2.2 and 5.7, respectively. This indicates a 1:1 and 1:2 morin/metal ratios at pH 2.2 and 5.7, respectively. Complete elution of the sorbed metal ions was carried out using 10mL (0.5molL(-1) HCl+0.01molL(-1) thiourea) in case of Au(III), Pd(II), Pt(II) and Rh(III) and 10mL 0.5molL(-1) HNO(3) in case of Ag(I). Morin-APSG was successfully employed in the separation and preconcentration of the investigated precious metal ions from some spiking water samples yielding 100-folds concentration factor. The relative standard deviation (R.S.D.) and the T-test (|t|(1)) were calculated.