改性纳米二氧化钛分离富集电感耦合等离子体原子发射光谱法测定地质样品中金钯铑

纳米TiO2用二苯基硫脲修饰后得到改性纳米TiO2,改性纳米TiO2对Au3+、Pd2+和Rh3+有很强的吸附能力,被用于Au3+、Pd2+和Rh3+分离富集。将该分离富集方法与电感耦合等离子体原子发射光谱法(ICP AES)相结合建立了测定地质样品中Au、Pd和Rh的新方法。考察了溶液酸度、洗脱条件和干扰离子等因素对分析物的分离富集影响。结果表明,在pH 40,Au3+、Pd2+和Rh3+可被改性纳米TiO2定量富集,吸附率在95%以上;而K+、Na+、Ca2+、Mg2+、Zn2+、Ni2+、Ba2+、Co2+、Cd2+和Mn2+不被吸附,Fe2+、In3+和Ga3+部分被吸附,但对测定没有影响。吸附的贵金属离子可用20 g/L CS(NH2)2 和 2 mol/L HCl溶液完全洗脱。在优化的实验条件下,吸附剂对Au3+、Pd2+ 和Rh3+的吸附容量分别为2163 mg /g, 1282 mg/g和1956 mg/g。本法对Au3+、Pd2+和Rh3+的检出限(3σ)分别为：061 ng/mL, 058 ng/mL和189 ng/mL,样品测定结果的相对标准偏差(RSD)分别为17%, 26%和18 (n=11)。该法应用于标准样品(GBW07293)中Au3+、Pd2+和Rh3+的测定,测定值与认定值相符。     

Study on Anticoagulation Factor I from Agkistrodon Acutus Venom by Rare Earth Ion Probes

Ｓｎａｋｅｖｅｎｏｍｓｃｏｎｔａｉｎｃｏｍｐｌｅｘｐｒｏｔｅｉｎｓｗｈｉｃｈｐｏｓｓｅｓｓｖａｒｉｏｕｓｂｉｏｌｏｇｉｃａｌａｃｔｉｖｉｔｉｅｓ ,ｉｎ ｃｌｕｄｉｎｇａｃｌａｓｓｔｈａｔａｆｆｅｃｔｓｃｏａｇｕｌａｔｉｏｎｓｙｓｔｅｍｗｉｔｈｃｏａｇｕｌａｎｔｏｒａｎｔｉｃｏａｇｕｌａｎｔａｃｔｉｖｉｔｉｅｓ .Ａｎａｎｔｉｃｏａｇｕｌａｎｔｆａｃｔｏｒ (ＡＣＦ)ｗａｓｐｒｅｖｉｏｕｓｌｙｉｓｏ ｌａｔｅｄｆｒｏｍｔｈｅｖｅｎｏｍｏｆＡｇｋｉｓｔｒｏｄｏｎａｃｕｔｕｓｆｒｏｍｓｏｕｔｈｅｒｎＡｎｈｕ…     

Stability of Rare Earth Ion-N, N′-bis（2′-Pyridine）methyl-1,10-Phenanthroline-2,9-Dimethanmine Binary Complexes

1 ,10 Phenanthrolinehasbeenextensivelyusedasanazaheterocyclicchelateligandinbothanalyticalandpreparativecoordinationchemistry[1] .Asanim portantligand ,1,10 phenanthrolineunitplaysanim portantroleforthedevelopmentofthesupramolecularchemistry .Manynovelsupramolecularcompoundsin clude 1,10 phenanthrolineunit[2～ 4 ] .Furthermore ,consideringtheuniquecombinationofchemicalstabil ities ,redoxproperties ,luminescenceemissionandex citedstatelifetime ,derivativesof 1,10 phenanthrolinehaveplayedama…     

高频燃烧红外吸收法测定氮化硅铁中碳

称取0.2g样品,置于预先盛有(0.300±0.005)g锡粒的坩埚内,覆盖(0.400±0.005)g纯铁和(2.000±0.005)g钨粒进行分析,建立了高频燃烧红外吸收法测定氮化硅铁中碳含量的分析方法。实验中,考虑到氮化硅铁标准样品较少,故选择由0.04g氮化硅标准样品JCRM R008和0.16g纯铁标准样品GBW 01148a混合配制的氮化硅铁合成校准试样(w(C)=0.025 7%)与氮化硅铁标准样品GSB 03-2469-2008(w(C)=0.35%)来绘制校准曲线。方法中碳的线性范围为0.025%~0.35%,检出限为0.000 45%。由0.10g氮化硅标准样品JCRM R008和0.10g纯铁标准样品GBW 01148a混合配制氮化硅铁合成样品1,以及由0.08g氮化硅铁标准样品GSB 03-2469-2008和0.12g氮化硅标准样品JCRM R006混合配制氮化硅铁合成样品2,采用实验方法对其中碳进行测定,测定值与认定值基本一致。采用实验方法对氮化硅铁实际样品中的碳进行测定,所得结果的相对标准偏差(RSD,n=6)为1.2%~1.7%。     

1，2-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)乙二酮-[1，2]与三正辛基氧化膦协同萃取RE(Ⅲ)的性能和机理研究

研究了1，2-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)乙二酮-[1，2](H     

离子选择性电极-逆格氏作图法测定镁合金微弧氧化衰变电解液中氟离子浓度

提出了一种将含氟的待测液加到氟离子标准溶液中以测定待测液中氟离子的方法--离子选择性电极 逆格氏作图法,并用此法测定了 AZ91D镁合金微弧氧化衰变电解液中氟离子浓度。待测试液中干扰离子和干扰的消除方法研究表明,从镁合金基体迁移到强碱性微弧氧化电 解液中的Zn²⁺、Cu²⁺、Ni²⁺和Fe³⁺离子均以沉淀形式被过滤除去, Mg²⁺、Al³⁺等离子的干扰以离子 强度剂TISAB消除,SiO₃^2-和多余的Al³⁺离子分别用C₄O₆H₂KNa 和EDTA掩蔽,溶液中的OH^-、Na⁺和K⁺均不干扰 氟的测定。用本法测定了老化的镁合金微弧氧化电解液中的氟离子浓度,加标回收率在99.7%～101.9%之间。用本法和离子选择性电极 标准曲线法对两种镁合金试样的微弧氧化电解液中的氟离子浓度分别进行测定并对测定结果的精密度和准确度进行分析,表明本法的精密度 比离子选择性电极-标准曲线法有所提高,而两种方法的正确度一致。本法可用于氟离子质量浓度高于1.9 g/L的复杂溶液体系中氟离子的 直接测定。     

温度滴定法测定铝材表面处理废水中总酸度和铝离子浓度

铝材表面通常采取一些化学方法处理如酸处理以达到提高材料的防护性和功能性、扩大应用范围和延长使用寿命。铝材表面处理后所产生的废水中含有较高浓度的H+和Al3+,对二者含量进行有效监控,无论是在生产监控方面还是环境保护方面都具有很大意义。本文首次应用温度滴定方法对水溶液中的H+和Al3+进行定量检测,并将该方法应用到铝厂实际废水的检测中。结果表明,此方法的测定值与理论值或常规的手动滴定法的测定值相符。方法的加标回收率：H+和Al3+分别为998%和1041%。精密度试验中H+和Al3+测定结果的相对标准偏差（RSD,n=7）均小于2%。     

Green, orange, and red upconversion luminescence in Nd3+/Yb3+: Cs2NaGdCl6 powders under 785 nm laser excitation

Nd3+:Cs2NaGdCl6 and Nd3+, Yb3+:Cs2NaGdCl6 polycrystalline powder samples were prepared by Morss method E. Under 785 nm semiconductor laser pumping, the upconversion luminescence of Nd3+ ions in Cs2NaGdCl6 was investigated at room temperature, and three upconversion emissions near 538 nm (Green), 603 nm (Grange), and 675 nm (Red) were observed and assigned to 4G7/2→4I9/2, (4G7/2→4I11/2; 4G5/2→4I9/2), and (4G7/2→4I13/2; 4G5/2→4I11/2), respectively. The dependences of these upconverted emissions on laser power and Nd3+ ion con-eentration were investigated, to explore the upconversion mechanism. The effect of doping Yb3+ ions on the upconversion luminescence of Nd3+ in Cs2NaGdCl6 was also studied under 785 nm laser excitation. The energy transfer processes were discussed as the possible mecha-nism for the above upconversion emissions.     

Investigation on the Use of the Weakly Basic Polyacrylate AnionExchanger Amberlite IRA-68 for Sorption and Separation of Iminodiacetate Complexes of Rare Earth Elements

Based on the determined affinity series of rare earth element complexes with IMDA for the anion-exchangers, purification of macroquantities of Nd^3 from Y^3 , Sm^3 from Ho^3 , La^3 from Nd^3 and La^3 from Pr^3 on the weakly basic gel anion-exchanger Amberlite IRA-68 was studied. Using the presented method on 1 L of Amberlite IRA-68 in the acetate form, it is possible to obtain about 240 g Nd2O3 purified from Y2O3. Great difference in affinity of La^3 and Nd^3 as well as Pr^3 complexes for this anion-exchanger in the acetate form indicates the possibility of applying this process for purification of lanthanum on the increased scale. On 1 L of Amberihe IRA-68 in the acetate form it is possible to obtain about 1125 g La2O3 purified from Nd2O3. On the basis of these results it can be assumed that unique properties of polyacrylate anion-exchangers enable their application for separation of rare earth elements.     

电感耦合等离子体质谱法分析粉煤灰漂珠中稀土元素

为研究粉煤灰漂珠中稀土元素对环境的影响,减少二次污染,建立了一种压力密闭消解-电感耦合等离子体质谱法测定粉煤灰漂珠中Sc,La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb和Lu等15种稀土元素的方法。方法用于分析国家标准物质(GBW07103)中稀土元素,结果与认定值一致;用于分析粉煤灰样品中稀土元素并做加标回收实验,加标回收率在93.9%~104.2%之间。     

电感耦合等离子体原子发射光谱法测定土壤中水溶性硫酸根

通常采用EDTA滴定法测定土壤中水溶性硫酸根,但该法操作繁琐、分析周期较长。为了适应大批量样品分析,实验通过对振荡浸取温度、时间、频率的优化,选择室温为22~28℃时,使用新制备的去离子水采用回旋振荡方式对土壤样品振荡浸取10min,经高速冷冻离心机离心使固液完全分离,从而建立了电感耦合等离子体原子发射光谱法(ICP-AES)直接测定土壤中水溶性硫酸根的分析方法。在选定的测定条件下,硫酸根的质量浓度在0.1~500μg /mL范围内与其对应的发射强度呈线性关系,校准曲线的线性相关系数r=0.9999。方法的检出限为0.26μg/g。按照实验方法测定土壤有效态一级标准物质GBW07412a、GBW07414a、GBW07415a、GBW07417a、GBW07459、GBW07461中水溶性硫酸根,结果与认定值的相对误差(RE)为-4.8%~4.4%,相对标准偏差(RSD,n=12)均不大于3.3%,满足中华人民共和国地质矿产行业标准土地质量地球化学评价规范DZ/T 0295—2016的分析质量要求。选择雄安新区酸性、碱性土壤样品和土壤有效态一级标准物质GBW07413a、GBW07415a、GBW07416a、GBW07417a,分别按照实验方法和NY/T 1121.18—2006滴定法、GB 8538—2016离子色谱法进行测定,结果无显著性差异。     

Ultraviolet to visible frequency-conversion properties of rare earths doped glass ceramics

Nd3+,Eu3+ and Tb3+ ions doped transparent chlorophosphate glass ceramics were prepared and their frequency-conversion properties were studied. X-ray diffraction (XRD) patterns evidenced the formation of expected halide nanocrystals. The absorption,excitation and emission spectra investigation indicated that some of rare earth (RE) ions were trapped in low phonon energy halide nanocrystals,and therefore an efficient down frequency-conversion was observed. The comparative spectroscopic studies of RE doped samples suggested that the glass ceramics systems are potentially applicable as efficient ultraviolet to visible frequency-conversion photonics materials.     

Luminescence Properties of Rare Earth Ions in Cadmium Metasilicate

The luminescence properties of CdSiO3:RE^3 phosphors doped with various rare earth ions are reported. The series of rare earth ions doped CdSiO3 phosphors are prepared by the conventional high-temperature solid-state method, and characterized by XRD and photoluminescence (PL) spectra. The results of XRD measurement indicate that the products fired under 1050 ~C for 3 h have a good crystallization without any detectable amount of impure phase. The PL spectra measurement results show that CdSiO3 is a novel self-activated luminescent matrix. When rare earth ions such as Y^3 ,La^3 , Gd^3 , Lu^3 , Ce^3 , Nd^3 , Ho^3 , Er^3 , Tm^3 and Yb^3 are introduced into the CdSiO3 host, one broadband centered at about 420 nm resulted from traps can be observed. In the case of other earth ions which show emissions at the visible spectrum region, such as Pr^3 , Sm^3 , Eu^3 , Tb^3 and Dy3 , the mixture of their characteristic line emissions with the ～420 nm strong broadband luminescence results in various emitting colors. As a consequence, different emitting colors can be attairied via introducing certain appropriate active ions into the CdSiO3 matrix. In additional, this kind of phosphors shows good long-lasting properties when excited by UV light. All the results show that CdSiO3 is a potential luminance matrix.     

Y2MgTiO6:Mn4+/Nd3+的制备及近红外发光性能

采用传统的高温固相反应制备了一系列Y₂MgTiO₆:Mn4+/Nd3+下转换材料。利用稳态激发发射光谱以及瞬态荧光寿命等进行了分析, 在Mn4+→Nd3+能量传递过程中, 在331 nm激发下Nd3+产生885 nm和1 085 nm的红外发射对应于4F_3/2→4I_11/2与4F_3/2→4I_9/2能级跃迁。研究结果证实, 双掺Mn4+/Nd3+的Y₂MgTiO₆在1 085 nm荧光强度比其单掺Nd3+的Y₂MgTiO₆增强了5倍。还进一步阐释了Mn4+→Nd3+能量传递主要是共振能量传递的偶极-偶极机制。近红外发光的下转换材料Y₂MgTiO₆:Mn4+/Nd3+对晶体硅太阳能电池的荧光转换层具有很好的应用价值。      

电感耦合等离子体原子发射光谱法测定石灰性土壤中有效磷

石灰性土壤中有效磷的测定通常采用钼锑抗分光光度法,操作复杂、检出限高。采用碳酸氢钠浸提-基体掩蔽结合电感耦合等离子体原子发射光谱法(ICP-AES)实现了对大批量土壤样本中有效磷的高效分析。实验中采用pH值为8.5、0.5 mol/L碳酸氢钠溶液为浸提液,按照20∶1的水土比(浸提液体积(mL)与土壤质量(g)之比)于(25±1)℃下振荡提取30 min;用定量滤纸过滤后,分取20.00 mL滤液,加入2 mL 硝酸(1+1)酸化,用250 mg的丁二酸掩蔽碱金属离子,选择P 214.914 nm为分析谱线,采用ICP-AES测定磷。结果表明,磷质量浓度与其发射强度在一定范围内呈良好的线性关系,线性相关系数为0.999 7。方法检出限为0.004 6 mg/kg,定量限为0.015 mg/kg。方法用于测定土壤标准物质(GBW07413a、GBW07414a、GBW07459、GBW07460、GBW07461)中有效磷,测定值与认定值基本相符,测定结果的相对标准偏差(RSD, n=6)为0.87%~2.1%;用于土壤样品中有效磷的测定,测定结果的相对标准偏差(n=6)不大于1.7%,与农业部标准方法(NY/T 1121.7—2014)测得的结果基本一致,无显著性差异。     

Effect of trivalent rare earth ions doping on the fluorescence properties of electron trapping materials SrS：Eu~（2＋）

Trivalent rare-earth ions (La3+,Pr3+,Nd3+,Sm3+,Gd3+,Tb3+,Dy3+,Ho3+,Er3+,Tm3+,and Yb3+) were investigated as the codoped auxiliary sensitizer for the electron trapping materials SrS:Eu2+ in order to enhance the fluorescence properties.It was found that Sm3+ and Tb3+ had the best photoluminescence stimulated luminescence (PSL) effect among the selected trivalent rare-earth ions.All the SrS:Eu2+ samples doped by different trivalent rare-earth ions could be stimulated by 980 nm laser after being exposed to the conventional sunlight,and they emitted PSL with the peak located at 615 nm.The result also indicated that some co-doped rare earth ions could increase fluorescence intensities of the traditional electron trapping materials SrS:Eu2+.     

电感耦合等离子体原子发射光谱法测定锡矿石中锡

分析锡含量的常用方法是极谱法,由于该方法在分析过程中需要使用汞,而汞常温下可蒸发为有剧毒的汞蒸气,因此有必要寻求一种安全、环保、快速的锡分析方法。本实验采用碱熔融法对锡矿石样品进行消解,建立了电感耦合等离子体原子发射光谱法(ICP-AES)对锡矿石中锡含量进行测定的方法。通过试验得出,采用过氧化钠熔样的最佳温度为670℃,熔样时间为7~10min,样品经热水提取后,经过30mL盐酸(1+1)进行酸化处理,然后采用1.00g酒石酸进行锡的络合,最后引入电感耦合等离子体原子发射光谱进行测定。采用实验方法对锡矿石标准物质GBW07281和GBW07282的检测结果与认定值基本相符,且测定结果的相对标准偏差(RSD,n=12)分别为1.8%和3.7%;对锡矿石实际样品进行测定,结果同传统的极谱法测定结果基本一致。实验方法满足矿山实验室准确快速的检测要求。     

电感耦合等离子体质谱法测定离子吸附型稀土矿中全相稀土总量

采用硝酸-氢氟酸-高氯酸混酸溶解试样,以电感耦合等离子体质谱法(ICP-MS)对试样溶解液进行测定,提出了以ICP-MS测定离子吸附型稀土矿中全相稀土总量的方法。对氢氟酸用量和测定液中硝酸的含量进行了考察,最终确定氢氟酸用量为5.0mL,测定液介质为体积分数为2%的硝酸。在优化的仪器条件下,15种单一稀土元素校准曲线的线性相关系数均大于0.9999,方法检出限为2.4μg/g。采用实验方法对稀土矿石国家标准物质GBW07158、GBW07160、GBW07161(用于标样制定的样品均采自江西省龙南离子吸附型稀土矿区)中的稀土总量进行测定,测定结果与认定值基本一致。将实验方法应用于稀土矿石国家标准物质GBW07159、GBW07160与离子吸附型稀土矿实际试样中稀土总量的测定,测得结果的相对标准偏差(RSD,n=11)为1.7%~3.1%。     

Investigation on 1.07 μm laser emission in Nd~（3＋）-doped sodium fluoroborate glasses

Spectroscopic and fluorescence properties of Nd 3+ ions in sodium fluoroborate(SFB) glasses were prepared and characterized through optical absorption,emission and decay measurements.The energy level analysis was carried out using free-ion Hamiltonian model.Experimental oscillator strengths were determined by measuring the area encompassed by the absorption peaks recorded for 1.0 mol.% Nd 3+-doped glasses.The Judd-Ofelt parameters(2,4,6) were used to evaluate the laser characteristic parameters such as radiative transition probability(A R),radiative decay time(τ R),fluorescence branching ratio(β R) and stimulated emission cross-section(σ e) for the 4 F 3/2 metastable state.The fluorescence spectra for different concentrations of Nd 3+ ions were recorded by exciting the samples at 514.5 nm Ar + ion laser.     

Complexation of N＇- [1-（3-aminophenyl）ethylidine] isonicotinohydrazide with La3＋, Pr3＋, Nd3＋, Sm3＋, Eu3＋ and Gd3＋ ions and associated thermodynamics

A novel Schiff base N′-[1-(3-aminophenyl)ethylidine]isonicotinohydrazide was prepared and its complexation behavior towards some selected lanthanides had been studied employing pH-metric and calorimetric titration and spectral techniques. pH-metric studies were carried out for the trivalent La, Pr, Nd, Sm, Eu, and Gd complexes in 30% aqueous-dioxane medium at constant ionic strength of 0.05 mol/L NaClO4 and at different temperatures of 293, 303 and 313 K. The proton-ligand formation constants of the ligand indicated the presence of only one dissociable proton while the metal-ligand formation constants were compatible with the formation of 1:1 Ln(Ⅲ) complexes. The sta-bility of the complexes followed the order: La3+Gd3+, showing a break at gadolinium. The thermodynamic parame-ters, ΔG, ΔH and ΔS associated with protonation and complexation reactions were negative which suggested that all reactions were exother-mic and enthalpy-driven. Isothermal calorimetric studies of Gd3+-aeINH systems at 303 K also showed exothermic nature of the complexation reaction and formation of 1:1 complex in agreement with the pH-metric data. Formation of 1:1 complexes was confirmed by the characteriza-tion of Nd(Ⅲ) complex. A seven coordinated geometry was assigned for the complex based on its elemental and spectral data.