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1.
夏强  廖小刚  沈海丽  郑林  李纲  田甜 《无机化学学报》2022,38(11):2191-2201
分别采用尿素水热-煅烧法、化学浴沉积-煅烧法和草酸盐热解法制备出具有不同形貌的Co3O4(Co3O4-A、Co3O4-B和Co3O4-C) 粉体材料,对比了它们作为催化剂活化过一硫酸盐(PMS)降解亚甲基蓝(MB)的性能。结果表明,3种Co3O4材料均具有分级微/纳米结构,形貌分别呈绒球状、无规则颗粒状和纤维状。PMS在3种催化剂作用下的分解过程均符合一级反应动力学模型,反应速率常数依次为0.047 1、0.217 4和0.003 7 min-1。无规则颗粒状Co3O4-B表现出最高的PMS活化性能,是其具有最大比表面积、最高表面氧空位浓度以及表面羟基密度综合作用的结果。在催化剂用量0.02 g·L-1、PMS投加量0.6 mmol·L-1的工艺参数条件下,Co3O4-B/PMS高级氧化体系在25 min内对MB的降解即可达98.33%。电子顺磁共振测试证实Co3O4-B/PMS高级氧化体系中存在·SO4-、·OH、·O2-1O2四种活性氧物种,基于此提出了Co3O4-B活化PMS及降解MB的反应机理。  相似文献   

2.
通过静电纺丝法制备Mn4+掺杂的Co3O4复合纳米纤维,利用XRD、XPS、BET、SEM和电化学工作站等对材料的结构、成分、形貌和电化学性能进行表征与测试。研究发现,通过Mn4+掺杂,Co3O4复合纳米纤维的电化学性能得到明显改善。当nConMn=20∶2时,相应的复合纤维具有较大比表面积68 m2·g-1,而且该样品呈现出清晰的氧化还原峰,在1 A·g-1的电流密度下,放电比电容量为585 F·g-1,这比纯Co3O4纳米纤维的416 F·g-1,有显著提高;循环500圈电容保持率达到82.6%,而纯Co3O4纳米纤维则是76.4%。  相似文献   

3.
通过简易、可控的水热方法在泡沫镍基体上直接生长了核壳结构的阵列型Co3O4@δ-MnO2/Pt正极。阵列电极有利于电极的润湿、氧气的传输和Li2O2的负载。Co3O4@δ-MnO2/Pt正极对氧还原和氧析出反应具有高的催化性能,可促使Li2O2依附Co3O4@δ-MnO2/Pt阵列生长,从而保持阵列结构。该生长行为有利于Li2O2在充电时分解。以Co3O4@δ-MnO2/Pt为催化正极的锂氧电池显示出高的容量(在电流密度100 mA·g-1时容量为2 480 mAh·g-1),以及长的循环寿命(容量限定在500 mAh·g-1时,在200 mA·g-1电流密度下,可循环65次),该性能超过了使用Co3O4或Co3O4@δ-MnO2催化剂的电池。  相似文献   

4.
将Co3O4/ZnO针状纳米棒材料修饰到针灸针表面用于检测葡萄糖浓度的变化。首先采用水热法在针灸针表面得到 Co(CO30.5(OH)·0.11H2O针状纳米棒前驱体,然后在500 ℃条件下退火3 h得到Co3O4针状纳米棒阵列。再采用浸渍法将预制备好的ZnO量子点修饰到Co3O4针状纳米棒表面,得到Co3O4/ZnO复合修饰的针灸针。研究发现此针灸针对葡萄糖具有较好的电流响应(2 264.27 μA·L·mmol-1·cm-2)、较快的响应速度(<4 s)及较低的检测极限(0.311 μmol·L-1S/N=3))。且该针灸针在用于检测人体模拟细胞液中葡萄糖浓度时,对抗坏血酸和尿素等表现出较强的抗干扰性。  相似文献   

5.
将Co3O4/ZnO针状纳米棒材料修饰到针灸针表面用于检测葡萄糖浓度的变化。首先采用水热法在针灸针表面得到Co(CO30.5(OH)·0.11H2O针状纳米棒前驱体,然后在500 ℃条件下退火3 h得到Co3O4针状纳米棒阵列。再采用浸渍法将预制备好的ZnO量子点修饰到Co3O4针状纳米棒表面,得到Co3O4/ZnO复合修饰的针灸针。研究发现此针灸针对葡萄糖具有较好的电流响应(2 264.27 μA·L·mmol-1·cm-2)、较快的响应速度(<4 s)及较低的检测极限(0.311 μmol·L-1S/N=3))。且该针灸针在用于检测人体模拟细胞液中葡萄糖浓度时,对抗坏血酸和尿素等表现出较强的抗干扰性。  相似文献   

6.
由高温固相反应制得Sr0.955Al2Si2-xTixO8:Eu2+x=0~1.0)系列试样,研究了Ti4+置换Si4+对其晶体结构和光谱特性的影响。Ti4+以类质同相替代Si4+进入晶体晶格中,形成了连续固溶体,其晶胞参数a,b,c,β和晶胞体积V随Ti4+置换量呈线性递增。Ti4+置换Si4+对晶胞参数c的影响显著,b其次,a最小。荧光激发谱为宽带,位于230~400nm,由267nm、305nm、350nm和375nm 4个峰拟合成,表观峰值位于351nm;随着Ti4+置换量的增加,半高宽(FWHM)从105nm减小到93nm。发射光谱位于380~600nm,表观峰值位于407nm,可由406nm和441nm两峰拟合而成并且随Ti4+置换量增加线性红移,Ti4+进入晶格对长波长发射中心影响较少;Ti4+置换量为1.0时,表观发射峰位从407nm红移至417nm;利用试样荧光光谱和VanUitert经验公式,得出SrAl2Si2O8:Eu2+中Sr2+的配位数为9。随着Ti4+置换量Si4+进入基质晶格,造成Eu-O距离变小,使得Eu2+所处的晶体场强度增强,发光中心Eu2+的5d能级分裂增大,造成Eu2+最低发射能级重心下移,两拟合谱峰峰位均呈线性红移。  相似文献   

7.
王飞  田一光  张乔 《无机化学学报》2019,35(6):1085-1092
通过高温固相反应在弱还原气氛下制备了Sr0.955Al2-xBxSi2O8:0.025Eu2+x=0~0.9)一系列荧光粉,研究了B(Ⅲ)取代基质晶格中的Al(Ⅲ)对荧光粉晶体结构和Eu2+发光性能的影响。B(Ⅲ)以类质同相取代基质晶格中Al(Ⅲ),形成了连续固溶体。随着B(Ⅲ)取代量的增加,荧光粉的晶胞参数(a、b、c)和晶胞体积(V)呈线性递减,而晶胞参数(β)呈线性递增。荧光粉的激发光谱为位于225~400 nm的宽峰,表观峰值位于350 nm,激发峰的半高宽(FWHM)随着B(Ⅲ)取代量的增加,从90 nm减小到102 nm。发射光谱位于370~600 nm的宽峰,可拟合为409和447 nm两个峰,表观峰值位于409 nm。随着B(Ⅲ)取代量的增加,2个拟合峰位均出现蓝移且2个峰强度比呈线性递减。根据试样荧光光谱,通过Van Uitert经验公式计算得出SrAl2Si2O8:Eu2+中Sr2+的配位数为9。随着B(Ⅲ)取代Al(Ⅲ)进入基质晶格,造成发光中心Eu与配体O距离增加,使得Eu2+所处的晶体场强度减小,发光中心Eu2+的5d能级分裂减小,造成Eu2+最低发射能级重心上移,2个拟合谱峰峰位均呈线性蓝移。  相似文献   

8.
周诗晖  王喆  张占辉 《无机化学学报》2023,39(12):2311-2316
采用高温固相法制备了2个系列的荧光粉样品:Ba2-xZnGe2O7xBi3+(系列Ⅰ)和Ba1.994-yKyZnGe2O7:0.006Bi3+(系列Ⅱ)。X射线衍射(XRD)测试结果表明,少量Bi3+、K+的掺杂不会明显改变材料的物相结构。样品的荧光光谱测试结果表明,虽然2个系列样品的发光光谱都随组成成分变化有少量变化,但发光颜色基本上均为黄绿色。在358 nm的激发下,荧光粉的发射光谱呈现一个峰值在500 nm的宽发射带,归属于3P11S0能级跃迁。在500 nm监测下,荧光粉的最强激发峰位于358 nm,归属于1S03P1能级跃迁,此外还有一个位于320 nm的肩峰归属于O2--Bi3+电荷转移带。系列Ⅰ样品的光谱数据结果指出,Bi3+的最佳掺杂量x为0.006。在该基质中,Bi3+掺杂取代Ba2+属于不等价取代,会在晶格中产生Ba2+空位或间隙O2-,对材料的发光强度产生负面影响。对此,采用K+与Bi3+协同掺杂起到电荷补偿的作用,填补Ba2+空位或捕获间隙O2-缺陷。空位被填补或间隙被捕获均减少了晶格畸变,从而使发光强度明显提高。系列Ⅱ样品的光谱数据表明,完全电荷补偿的荧光粉样品相比于没有掺K+的样品,其发光强度提高了约2.5倍。  相似文献   

9.
采用沉淀法和浸渍法制备了2种铬基(Cr2O3和CrO3/Cr2O3)催化剂,用于气相氟化2-氯-1,1,1-三氟乙烷合成1,1,1,2-四氟乙烷。研究发现含有低价铬(Cr3+)物种的Cr2O3催化剂上2-氯-1,1,1-三氟乙烷的稳态转化率为18.5%,而含有高价铬(Cr6+)物种和低价铬(Cr3+)物种的CrO3/Cr2O3催化剂初始转化率达到30.6%,然而存在明显的失活。含有Cr6+物种的CrO3/Cr2O3催化剂的2-氯-1,1,1-三氟乙烷氟化反应初始TOF值为1.71×10-4 molHCFC-133a·molCr(Ⅵ)-1·s-1,高于含有Cr3+物种的Cr2O3催化剂(4.16×10-5 molHCFC-133a·molCr(Ⅲ)-1·s-1)。Cr2O3催化剂在氟化反应前后催化剂的物相结构保持不变;而含有高价铬物种的CrO3/Cr2O3催化剂经HF反应后生成了CrOxFy活性物种。然而,CrOxFy物种在反应中挥发或转化成稳定但无活性的CrF3,从而导致催化剂失活。  相似文献   

10.
采用共沉淀法及1 200 ℃后续煅烧4 h,成功制备了CaSb2O6:Bi3+,Eu3+荧光粉,并对其结构及发光性能进行了研究。所制备荧光粉颗粒为六边形类圆饼状,平均尺寸在100~600 nm之间。对CaSb2O6:Bi3+,Eu3+发光的机理分析表明,Bi3+对Eu3+的发光存在高效的敏化与能量传递。当Bi3+和Eu3+的掺杂浓度分别为0.5%和8%,Eu3+位于580 nm(5D07F0 )处的荧光发射显著增强,Bi3+,Eu3+共掺样品的荧光强度是CaSb2O6:Eu3+的10倍左右。调节Bi3+/Eu3+离子掺杂比,色坐标呈现了从蓝、白光到红光的变化,表明该荧光粉可分别作为蓝或红色荧光粉使用,甚至可实现从蓝、白光到红光的自由调控,这为白光LED荧光粉的发展提供了参考。  相似文献   

11.
K3InF6 is synthesized by a sol-gel route starting from indium and potassium acetates dissolved in isopropanol in the stoichiometry 1:3, with trifluoroacetic acid as fluorinating agent. The crystal structures of the organic precursors were solved by X-ray diffraction methods on single crystals. Three organic compounds were isolated and identified: K2InC10O10H6F9, K3InC12O14H4F18 and K3InC12O12F18. The first one, deficient in potassium in comparison with the initial stoichiometry, is unstable. In its crystal structure, acetate as well as trifluoroacetate anions are coordinated to the indium atom. The two other precursors are obtained, respectively, by quick and slow evaporation of the solution. They correspond to the final organic compounds, which give K3InF6 by decomposition at high temperature. The crystal structure of K3InC12O14H4F18 is characterized by complex anions [In(CF3COO)4(OHx)2](5−2x)− and isolated [CF3COOH2−x](x−1)− molecules with x=2 or 1, surrounded by K+ cations. The crystal structure of K3InC12O12F18 is only constituted by complex anions [In(CF3COO)6]3− and K+ cations. For all these compounds, potassium cations ensure only the electroneutrality of the structure. IR spectra of K2InC10O10H6F9 and K3InC12O12F18 were also performed at room temperature on pulverized crystals.  相似文献   

12.
一些具有NASICON型网格结构的固体电解质具有高的电导率和好的稳定性,NASICON的意思是Na Super Ionic Conductor[1]。当NaZr2(PO4)3中P5 被Si4 部分取代时便可以得到具有NASICON结构的Na1 xZr2SixP3-xO12体系,其具有高的钠离子电导率。然而有相同结构的Li1 xZr2SixP3-xO12体系的离子电导率却很低,这是因为Li 半径太小,而NASICON三维网格结构的离子通道太大,两者不匹配而使电导率下降[2]。但当LiZr2(PO4)3中Zr4 被离子半径小些的Ti4 取代,所得LiTi2(PO4)3的通道就与Li 半径相匹配,适合于锂离子的迁移,从而使其电导率…  相似文献   

13.
The compound previously reported as Ba2Ti2B2O9 has been reformulated as Ba3Ti3B2O12, or Ba3Ti3O6(BO3)2, a new barium titanium oxoborate. Small single crystals have been recovered from a melt with a composition of BaTiO3:BaTiB2O6 (molar ratio) cooled between 1100°C and 850°C. The crystal structure has been determined by X-ray diffraction: hexagonal system, non-centrosymmetric space group, a=8.7377(11) Å, c=3.9147(8) Å, Z=1, wR(F2)=0.039 for 504 unique reflections. Ba3Ti3O6(BO3)2 is isostructural with K3Ta3O6(BO3)2. Preliminary measurements of nonlinear optical properties on microcrystalline samples show that the second harmonic generation efficiency of Ba3Ti3O6(BO3)2 is equal to 95% of that of LiNbO3.  相似文献   

14.
A new oxide, Bi14Sr21Fe12O61, with a layered structure derived from the 2212 modulated type structure Bi2Sr3Fe2O9, was isolated. It crystallizes in the I2 space group, with the following parameters: a=16.58(3) Å, b=5.496(1) Å, c=35.27(2) Å and β=90.62°. The single crystal X-ray structure determination, coupled with electron microscopy, shows that this ferrite is the m=5 member of the [Bi2Sr3Fe2O9]m[Bi4Sr6Fe2O16] collapsed family. This new collapsed structure can be described as slices of 2212 structure of five bismuth polyhedra thick along , shifted with respect to each other and interconnected by means of [Bi4Sr6Fe2O16] slices. The latter are the place of numerous defects like iron or strontium for bismuth substitution; they can be correlated to intergrowth defects with other members of the family.  相似文献   

15.
The ferroelectric ceramics of Bi4Ti3O12, SrBi4Ti4O15, and lanthanum-doped Bi4Ti3O12-SrBi4Ti4O15 were synthesized, and their Raman spectra were investigated. La-doping resulted in the enlargement of remnant polarization of Bi4Ti3O12-SrBi4Ti4O15. The structure of the Bi2O2 layers and TiO6 octahedra of the intergrowth was found to be different from those of Bi4Ti3O12 and SrBi4Ti4O15. La3+ ions exhibit pronounced selectivity for the occupation of A site as La content is lower than 0.50, and tend to be incorporated into Bi2O2 layers when the La content is higher than 0.50. Lanthanum substitution brings about the structural phase transition in Bi4Ti3O12-SrBi4Ti4O15. The variation of ferroelectric property may be attributed to combined contribution from the decreasing of the oxygen vacancies, the relaxation of the lattice distortion, the destroying of the insulation and the space charge compensation effects of the Bi2O2 slabs.  相似文献   

16.
Thin crystals of La2O3, LaAlO3, La2/3TiO3, La2TiO5, and La2Ti2O7 have been irradiated in situ using 1 MeV Kr2+ ions at the Intermediate Voltage Electron Microscope-Tandem User Facility (IVEM-Tandem), Argonne National Laboratory (ANL). We observed that La2O3 remained crystalline to a fluence greater than 3.1×1016 ions cm−2 at a temperature of 50 K. The four binary oxide compounds in the two systems were observed through the crystalline-amorphous transition as a function of ion fluence and temperature. Results from the ion irradiations give critical temperatures for amorphisation (Tc) of 647 K for LaAlO3, 840 K for La2Ti2O7, 865 K for La2/3TiO3, and 1027 K for La2TiO5. The Tc values observed in this study, together with previous data for Al2O3 and TiO2, are discussed with reference to the melting points for the La2O3-Al2O3 and La2O3-TiO2 systems and the different local environments within the four crystal structures. Results suggest that there is an observable inverse correlation between Tc and melting temperature (Tm) in the two systems. More complex relationships exist between Tc and crystal structure, with the stoichiometric perovskite LaAlO3 being the most resistant to amorphisation.  相似文献   

17.
The two new compounds, Sr4Cu3(AsO4)2(AsO3OH)4·3H2O (1) and Ba2Cu4(AsO4)2(AsO3OH)3(2), were synthesized under hydrothermal conditions. They represent previously unknown structure types and are the first compounds synthesized in the systems SrO/BaO-CuO-As2O5-H2O. Their crystal structures were determined by single-crystal X-ray diffraction [space group C2/c, a=18.536(4) Å, b=5.179(1) Å, c=24.898(5) Å, β=93.67(3)°, V=2344.0(8) Å3, Z=4 for 1; space group P42/n, a=7.775(1) Å, c=13.698(3) Å, V=828.1(2) Å3, Z=2 for 2]. The crystal structure of 1 is related to a group of compounds formed by Cu2+-(XO4)3− layers (X=P5+, As5+) linked by M cations (M=alkali, alkaline earth, Pb2+, or Ag+) and partly by hydrogen bonds. In 1, worth mentioning is the very short hydrogen bond length, D···A=2.477(3) Å. It is one of the examples of extremely short hydrogen bonds, where the donor and acceptor are crystallographically different. Compound 2 represents a layered structure consisting of Cu2O8 centrosymmetric dimers crosslinked by As1φ4 tetrahedra, where φ is O or OH, which are interconnected by Ba, As2 and hydrogen bonds to form a three-dimensional network. The layers are formed by Cu2O8 centrosymmetric dimers of CuO5 edge-sharing polyhedra, crosslinked by As1O4 tetrahedra. Vibrational spectra (FTIR and Raman) of both compounds are described. The spectroscopic manifestation of the very short hydrogen bond in 1, and ABC-like spectra in 2 were discussed.  相似文献   

18.
利用类石墨氮化碳(g-C_3N_4)和亚稳相钙钛氧化物(CaTi_2O_5)固相法制备C_3N_4/CaTi_2O_5复合材料。利用X射线衍射(XRD)、金相显微镜、扫描电子显微镜(SEM)及附带能谱分析仪(EDS)和N2吸附-脱附对样品的显微结构和比表面积进行检测分析,并用紫外-可见吸收光度计(UV-Vis)测试了样品的光吸收性能,研究C_3N_4与CaTi_2O_5物质的量之比(nC_3N_4/nCaTi_2O_5)对C_3N_4/CaTi_2O_5复合样品的物相结构和微观形貌的影响,同时考察C_3N_4/CaTi_2O_5复合样品在可见光照射下光催化降解罗丹明染料效果。实验结果表明:相比纯C_3N_4和CaTi_2O_5样品,C_3N_4/CaTi_2O_5复合样品在可见光下具有较高的光催化性能,随着nC_3N_4/nCaTi_2O_5增加,样品的光催化降解率随之增加而后降低,当nC_3N_4/nCaTi_2O_5=1∶1时,样品的光催化降解率达到最大值99.5%,并且循环重复利用5次后,样品的光催化剂降解率仍几乎保持不变。复合样品光催化性能提高主要归因于复合能级结构有效地抑制了电子和空穴复合所致。  相似文献   

19.
Magnetic diphase nanostructures of ZnFe2O4/γ-Fe2O3 were synthesized by a solvothermal method. The formation reactions were optimized by tuning the initial molar ratios of Fe/Zn. All samples were characterized by X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, and Raman spectra. It is found that when the initial molar ratio of Fe/Zn is larger than 2, a diphase magnetic nanostructure of ZnFe2O4/γ-Fe2O3 was formed, in which the presence of ZnFe2O4 enhanced the thermal stability of γ-Fe2O3. Further increasing the initial molar ratio of Fe/Zn larger than 6 destabilized the diphase nanostructure and yielded traces of secondary phase α-Fe2O3. The grain surfaces of diphase nanostructure exhibited a spin-glass-like structure. At room temperature, all diphase nanostructures are superparamagnetic with saturation magnetization being increased with γ-Fe2O3 content.  相似文献   

20.
利用类石墨氮化碳(g-C3N4)和亚稳相钙钛氧化物(CaTi2O5)固相法制备C3N4/CaTi2O5复合材料。利用X射线衍射(XRD)、金相显微镜、扫描电子显微镜(SEM)及附带能谱分析仪(EDS)和N2吸附-脱附对样品的显微结构和比表面积进行检测分析,并用紫外-可见吸收光度计(UV-Vis)测试了样品的光吸收性能,研究C3N4与CaTi2O5物质的量之比(nC3N4/nCaTi2O5)对C3N4/CaTi2O5复合样品的物相结构和微观形貌的影响,同时考察C3N4/CaTi2O5复合样品在可见光照射下光催化降解罗丹明染料效果。实验结果表明:相比纯C3N4和CaTi2O5样品,C3N4/CaTi2O5复合样品在可见光下具有较高的光催化性能,随着nC3N4/nCaTi2O5增加,样品的光催化降解率随之增加而后降低,当nC3N4/nCaTi2O5=1:1时,样品的光催化降解率达到最大值99.5%,并且循环重复利用5次后,样品的光催化剂降解率仍几乎保持不变。复合样品光催化性能提高主要归因于复合能级结构有效地抑制了电子和空穴复合所致。  相似文献   

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