电纺Pd纳米粒子/碳纳米纤维复合材料对甲醇的电催化氧化研究

利用静电纺丝技术制备了含有乙酰丙酮钯(Pd(Ac)2)前体的聚丙烯腈(PAN)纳米纤维,经H2还原和900℃碳化处理得到了Pd纳米粒子负载的碳纳米纤维复合材料(Pd/CNF).此方法中,CNF的制备和Pd纳米粒子的形成是同步进行的,无需对碳载体进行任何预处理,实现了纳米粒子负载CNF的一步制备,简化了实验步骤的同时确保CNF载体骨架的完整性.扫描电镜(SEM)和透射电镜(TEM)分析表明,大小均一的Pd纳米粒子牢固地分散在CNF表面,其粒径约为60 nm.X-射线衍射(XRD)和X-射线光电子能谱(XPS)表征了Pd/CNF的晶体结构.Pd纳米粒子以单质态形式存在,具有面心立方体结构.通过循环伏安法(CV)和计时电流法等电化学方法研究了Pd/CNF复合材料对甲醇的电催化氧化情况,Pd/CNF对甲醇氧化显示出优异的催化活性和稳定性,优于商业化Pd/C催化剂.     

介孔碳化钨纳米片团簇的制备及其电催化析氢性能

采用阳极氧化法与原位还原碳化法相结合,在电击穿条件下可控制备了具有介孔结构的碳化钨纳米片团簇(WC NFs)。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、N₂吸附-脱附测试表征其物相、微观结构和孔径分布。在1 mol·L^-1H₂SO₄溶液中采用线性扫描伏安法、循环伏安法、计时电流法以及交流阻抗谱测试催化剂的电化学性能。结果表明,在650℃下还原碳化所制备的WC NFs具有最佳的电催化析氢性能,在电流密度为10 mA·cm^-2时过电位η₁₀仅为150 mV,Tafel斜率为56 mV·dec^-1,并具有良好的循环稳定性。     

Pd/PdO纳米复合微球的合成及催化性能

采用甲基丙烯酸锌加速还原氯化钯(PdCl₂) 溶液中的钯离子(Pd ²⁺)为钯(Pd) 纳米微球, 进而用得到的钯纳米微球直接制备钯/氧化钯(Pd/PdO) 纳米复合微球. 通过扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 粉末X射线衍射分析(XRD)及X射线光电子能谱分析(XPS) 等方法对 Pd/PdO 纳米复合微球进行表征, 结果表明, 制备的纳米复合微球为表面粗糙、 大小均一的纳米微球. 采用紫外-可见吸收光谱(UV-Vis) 等方法考察了 Pd/PdO 纳米复合微球在对硝基苯酚(4-NTP) 还原反应中的催化性能, 发现其具有良好的催化活性和循环稳定性.     

聚多巴胺包覆银衍生氧还原电催化剂的合成

以聚多巴胺(PDA)为载体,利用多巴胺的还原性在碱性条件下还原硝酸银,再经过高温热解,使聚多巴胺碳化,合成了Ag@C-PDA催化剂.这种催化材料在氧还原反应(ORR)相关的测试当中有较好的表现,在0.1 mol·L^-1的KOH电解质中起始电位和半波电位分别为0.879和0.731 V(νs. RHE),在电势为0.4 V时,其动力学极限电流密度可达到4.81 mA·cm^-2.经过20 000 s的i-t循环后,Ag@C-PDA催化剂的电流衰减仅为3%,表现出了优于商业Pt/C的稳定性.Ag@C-PDA良好的ORR电化学活性源于本身具有较强导电性的Ag纳米粒子均匀分散以及碳材料较高的石墨化程度.     

AOPAN/PA-66复合纳米纤维膜的制备及对金属离子的吸附性能

采用双喷头电纺丝技术,将尼龙(PA-66)纤维增强的聚丙烯腈(PAN)纳米纤维膜(PAN/PA-66)与盐酸羟胺进行偕胺肟化反应,制备了一种偕胺肟化聚丙烯腈/尼龙复合纳米纤维膜(AOPAN/PA-66).通过红外光谱及扫描电子显微镜等方法研究了偕胺肟化前后纳米纤维膜的组成、形貌和力学性能;并考察了AOPAN/PA-66复合纳米纤维膜对铜离子和铅离子的吸附性能.结果表明,AOPAN/PA-66复合纳米纤维膜的抗拉伸强度及断裂伸长率分别为4.73 MPa和30.76%,对Cu(Ⅱ)及Pb(Ⅱ)的吸附量分别为67.5和75.4 mg/g.     

三维交联石墨烯纳米纤维的合成及储锂性能

以氧化石墨烯为原料,高温下自组装得到高结晶的三维交联石墨烯纳米纤维.扫描电子显微镜和透射电子显微镜观测结果表明,三维石墨烯纳米纤维为实心结构,直径小于100 nm,石墨烯片层有序排列卷曲,具有较高的结晶度.电化学性能研究结果表明,该纳米纤维作为锂离子电池负极材料时,展现出较高的首次库仑效率(72. 4%)与储锂容量(0. 1C倍率下容量为692. 7 m A·h/g)、良好的倍率性能(20C倍率下容量为373. 3 m A·h/g)及优异的循环稳定性(1000次循环后容量保持率为84. 1%).     

UiO-66/CoSO4复合材料对环境中盐酸左氧氟沙星的高效去除

以UiO-66为前驱体制得UiO-66/CoSO₄复合材料，借助扫描电子显微镜、透射电子显微镜、元素分析和比表面积分析等手段对复合材料的微观形貌和结构进行表征，采用吸附平衡实验，系统考察该复合材料的吸附性能.结果表明，在相同条件下UiO-66/CoSO₄复合材料比UiO-66对盐酸左氧氟沙星的去除率提高26.5%，且复合材料在30 min对盐酸左氧氟沙星的吸附达到平衡，最大吸附容量为108.4 mg·g^-1，其吸附特性符合假二级动力学模型.该UiO-66/CoSO₄复合材料制备过程简单，对实际环境水样和土样中盐酸左氧氟沙星的去除率在94.7%以上，且经过5次再生循环使用后，吸附效率无明显下降.     

钯/碳纳米纤维复合材料修饰电极同时检测邻苯二酚和对苯二酚

利用电纺丝技术制得钯/碳纳米纤维复合材料(Pd/CNFs),并将其用于修饰玻碳电极Pd/CNF-GCE/CME.Pd/CNF-GCE/CME对邻苯二酚和对苯二酚的氧化还原反应具有较高的电催化活性,显著提高了二者电化学反应的可逆性.考察了支持电解质的酸度对邻苯二酚和对苯二酚电化学响应的影响,选用0.1 mol/L PBS(pH 8.0)作为支持电解质.用微分脉冲伏安(DPV)法对邻苯二酚和对苯二酚进行选择性检测:当混合溶液中存在50 μmol/L对苯二酚时,邻苯二酚的氧化峰电流与其浓度在1～90 μmol/L范围内呈线性关系,检出限为0.3 μmol/L(S/N=3);当存在50 μmol/L邻苯二酚时,对苯二酚的氧化峰电流与其浓度在2～100 μmol/L范围内呈线性关系,检出限为1.0 μmol/L.另外,此修饰电极具有较好的重现性和较强的抗干扰能力.将此修饰电极用于模拟水样中邻苯二酚和对苯二酚的测定,结果令人满意.     

碳纳米纤维负载铁镍合金在锌空气电池中的应用

析氧反应(OER)催化剂在锌空气电池(ZABs)储能过程中起着关键作用。我们开发了一种新型非贵金属基自支撑碳纳米纤维催化剂(Ni_δFe_4-δ-CNF)。首先,以聚乙烯吡咯烷酮、过渡金属乙酸酯、N,N-二甲基甲酰胺为原料,采用静电纺丝法制备了网状前驱体。随后,通过高温退火处理,将其转化为三维(3D)多孔结构材料。合成的Ni₁Fe₁-CNF催化剂在浓度为1 mol·L^-1KOH的电解质溶液中具有较低的起始电位(230 m V)和过电势(280 mV,10 mA·cm^-2),性能优于商业RuO₂。同时,将Ni₁Fe₁-CNF催化剂与商业Pt/C催化剂混合,作为空气阴极催化剂组装成ZAB,与商业的RuO₂+Pt/C ZAB相比,Ni₁Fe₁-CNF+Pt/C ZAB具有更高的功率密度(122 m W·cm^-2)、...     

静电纺丝制备多孔碳纳米纤维及其电化学电容行为

采用静电纺丝技术,以聚丙烯腈(PAN)/醋酸锌为前驱体制备复合纳米纤维,随后经碳化、酸化获得多孔碳纳米纤维.扫描电子显微镜(SEM)观察发现,碳纳米纤维表面分布大量孔洞.N2吸脱附等温曲线(BET)测试材料比表面积达413m2·g-1.循环伏安法(CV)和恒流充放电(CP)性能测试表明:多孔碳纳米纤维具有较好的电化学性能,在1A·g-1的电流密度下比电容达275F·g-1.相比碳纳米纤维比容量提高了162%.     

氮化钨-钨/掺氮有序介孔碳复合材料的制备及其氧还原性能

采用软模板法制备了氮化钨-钨/掺氮有序介孔碳复合材料(WN-W/NOMC),作为一种高比表面积且价格低廉的阴极氧还原反应催化剂。通过适量添加尿素来改变复合材料中的氮含量,在掺氮量为7%(w/w)时,实验发现材料能够保持完整有序介孔结构,测试其比表面积高达835 m~2·g~(-1),透射电子显微镜(TEM)测试结果显示其催化颗粒均匀地分散在氮掺杂有序介孔碳载体上。在O_2饱和的0.1 mol·L~(-1 )KOH溶液中测试了材料的氧还原催化性能(ORR),显示其起始电位为0.87 V(vs RHE),极限电流密度为4.49 mA·cm~(-2),氧还原反应的转移电子数为3.4,接近于20%(w/w)商业Pt/C的3.8,说明该材料表现出近似4电子的氧还原反应途径。研究结果表明,WN-W/NOMC的催化性能虽然稍弱于商业铂碳(0.99 V,5.1 mA·cm~(-2)),但其具有远超铂碳的循环稳定性和耐甲醇毒化能力。     

Nanosized anatase titanium dioxide loaded porous carbon nanofiber webs as anode materials for lithium-ion batteries

Nanosized anatase titanium dioxide loaded porous carbon nanofibers (TiO₂/PCNFs) were prepared from electrospun TiO(OAc)₂/PAN/PMMA composite precursor fibers with different amount of PMMA porogen, which were sequentially heat-treated in different environments. Electrochemical measurement results show that these as-prepared TiO₂/PCNFs present higher cyclic reversible capacity than the TiO₂/CNFs counterpart (without PMMA porogen in its precursor fibers). Among the as-prepared TiO₂/PCNFs samples, the representative TiO₂/PCNFs (the mass ratio of PAN to PMMA is 3:1) exhibits the best high-rate performance with a high stable capacity retention about 200 mAhg^{− 1} at a current density as high as 800 mAg^{− 1}. This novel TiO₂/PCNFs composite material opens up a promising application in high-power lithium-ion batteries.     

氮化钨-钨/掺氮有序介孔碳复合材料的制备及其氧还原性能

采用软模板法制备了氮化钨-钨/掺氮有序介孔碳复合材料（WN-W/NOMC）,作为一种高比表面积且价格低廉的阴极氧还原反应催化剂。通过适量添加尿素来改变复合材料中的氮含量,在掺氮量为7%（w/w）时,实验发现材料能够保持完整有序介孔结构,测试其比表面积高达835 m²·g^-1,透射电子显微镜（TEM）测试结果显示其催化颗粒均匀地分散在氮掺杂有序介孔碳载体上。在O₂饱和的0.1 mol·L^-1 KOH溶液中测试了材料的氧还原催化性能（ORR）,显示其起始电位为0.87 V（vs RHE）,极限电流密度为4.49 mA·cm^-2,氧还原反应的转移电子数为3.4,接近于20%（w/w）商业Pt/C的3.8,说明该材料表现出近似4电子的氧还原反应途径。研究结果表明,WN-W/NOMC的催化性能虽然稍弱于商业铂碳（0.99 V,5.1 mA·cm^-2）,但其具有远超铂碳的循环稳定性和耐甲醇毒化能力。     

Preparation and photocatalytic performance research of Bi2WO6/UiO-66-NH2 composite

Bi₂WO₆/UiO-66-NH₂ photocatalysts were fabricated through solvothermal method using acetic acid as template. The photocatalytic performance of as-fabricated composites was highly improved under simulated visible light due to the addition of UiO-66-NH₂. The structural and chemical properties of the composites were characterized through FTIR, XRD, XPS, SEM, BET, UV–vis DRS and PL. After 90 min of visible light irradiation, the RhB at an initial concentration of 10 mg·L^?1 in the solution was degraded by 99.4% due to the addition of 10 mg of the composite. There was no significant decrease in the photocatalytic activity even after four rounds of cycles. The free radical capture experiments indicate that the photogenerated holes (h⁺) were the main active sites. The possible photocatalytic degradation mechanism was proposed as the specific surface area of the composite was enlarged due to the uniform distribution of UiO-66-NH₂ on the surface of Bi₂WO₆. The electron–hole pairs recombination rate was decreased due to the photogenerated electrons (e^?) on the CB of Bi₂WO₆ which can be rapidly transferred to the CB of UiO-66-NH₂ and the photogenerated holes of UiO-66-NH₂ transferred to the VB of Bi₂WO₆. Meanwhile, the RhB was directly oxidized to H₂O and CO₂ by h⁺ to achieve the purification effect.

     

Selectivity Control in the Direct CO Esterification over Pd@UiO-66: The Pd Location Matters

The selectivity control of Pd nanoparticles (NPs) in the direct CO esterification with methyl nitrite toward dimethyl oxalate (DMO) or dimethyl carbonate (DMC) remains a grand challenge. Herein, Pd NPs are incorporated into isoreticular metal–organic frameworks (MOFs), namely UiO-66-X (X=-H, -NO₂, -NH₂), affording Pd@UiO-66-X, which unexpectedly exhibit high selectivity (up to 99 %) to DMC and regulated activity in the direct CO esterification. In sharp contrast, the Pd NPs supported on the MOF, yielding Pd/UiO-66, displays high selectivity (89 %) to DMO as always reported with Pd NPs. Both experimental and DFT calculation results prove that the Pd location relative to UiO-66 gives rise to discriminated microenvironment of different amounts of interface between Zr-oxo clusters and Pd NPs in Pd@UiO-66 and Pd/UiO-66, resulting in their distinctly different selectivity. This is an unprecedented finding on the production of DMC by Pd NPs, which was previously achieved by Pd(II) only, in the direct CO esterification.     

脊椎状NiCo2O4纳米棒的制备及其析氧和氧还原性能研究

以水热法并进一步焙烧合成脊椎状NiCo₂O₄纳米棒,通过透射电子显微镜（TEM）、X射线衍射仪（XRD）、X射线光电子能谱仪（XPS）和热重分析仪（TG）等来表征其结构形态及热稳定性.采用线性扫描法（LSV）、循环伏安（CV）研究所制备催化剂的在玻碳和旋转圆盘电极上的电催化活性：在0.1 mol·L^-1 KOH溶液中的电催化析氧反应（OER）和电催化氧还原反应（ORR）.研究结果表明,所制备的脊椎状NiCo₂O₄纳米棒有大量的不饱和态,200℃焙烧制备的脊椎状NiCo₂O₄纳米棒析氧过电位最小可达309 mV,Tafel斜率145.6 mV/dec,其氧还原极限电流密度在1600 rmp可达到5.095 mA·cm^-2,电子转移数在3.2~3.8之间,接近四电子转移机理,其优良电化学性能可能是由于暴露了更多的边缘缺陷的缘故.     

Attachment of Fe3O4 nanoparticles on UiO-66: A stable composite for efficient sorption and reduction of selenite from water

In the present work, Fe₃O₄ nanoparticles were attached to the surface of UiO-66, a zirconium-based metal–organic framework material and the composite material formed was used to remove selenite (Se(IV)) in water. The Fe₃O₄/UiO-66 composite were assembled by a facile two-stage strategy. Benefiting from the ultra-high specific surface area of UiO-66, the Fe₃O₄/UiO-66 also had a large specific surface area, which made it easier to expose the active sites of Fe₃O₄ on the surface of UiO-66. The XPS and Mössbauer spectroscopy analysis indicated that there was charge transfer between Fe₃O₄ and UiO-66 in the Fe₃O₄/UiO-66, which made the Fe₃O₄ on the surface of UiO-66 had enhanced reductive activity. The mechanism of Fe₃O₄/UiO-66 to removed Se(IV) from the solution was further investigated by Zeta potential, FT-IR, SEM, TEM, and XPS spectra. The results indicated that the Fe₃O₄ nanoparticles on the surface of UiO-66 not only interacted with selenite through electrostatic action and inner-sphere complex but could also reduce a large amount of selenite to the insoluble Se⁰. The combination of these three actions finally strengthened the removal of selenite. This study cloud promote the practical application of MOF-based composites in removing heavy metal ions.     

氮掺杂碳纤维负载镍钴硒化物的制备及其电催化析氢性能

以静电纺丝制备的纤维为前驱体,通过煅烧、硒化处理等工艺合成了负载双金属硒化物纳米粒子的氮掺杂碳纤维(NCF)材料((Ni,Co)Se2/NCF),并对其进行了一系列相关的表征,研究了其在酸性和碱性条件下的析氢性能.(Ni,Co)Se2纳米粒子被锚定于NCF中,有效地阻止了纳米粒子的聚集,提供了更多的催化活性位点.电催化...     

Chitosan/UiO-66 composites as high-performance adsorbents for the removal of methyl orange in aqueous solution

UiO-66 and chitosan/UiO-66 composites were successfully synthesized by varying the mass addition of chitosan which were 0%, 2.5%, 5%, 10%, and 20% of the mass of UiO-66, denoted as UiO-66, Cs(2.5)/UiO-66, Cs(5)/UiO-66, Cs(10)/UiO-66, and Cs(20)/UiO-66, respectively. UiO-66 was modified with chitosan using the impregnation process. The X-ray diffraction patterns of the synthesized materials showed characteristic peaks at 2θ of 7.25° and 8.39°, which matched to that of the reported UiO-66. In addition, the Fourier transform infrared spectroscopy spectra of the materials showed absorption bands at the same wavenumber as UiO-66 and chitosan previously reported. The surface morphology of UiO-66 observed from scanning electron microscopy images was in the form of agglomerated small cube particles, where the smaller particles were observed for Cs(10)/UiO-66. From the N₂ adsorption isotherms, it was found that the Brunauer-Emmett-Teller surface areas of UiO-66, Cs(5)/UiO-66, and Cs(10)/UiO-66 materials were 825.7 m²/g, 835.4 m²/g, and 882.2 m²/g, respectively. The results of the study on adsorption of methyl orange in aqueous solutions showed that Cs(5)/UiO-66 had the highest adsorption capacity of 370.37 mg/g and followed the pseudo–second-order adsorption kinetic with a Langmuir isotherm model.     

ZIF67衍生硫化钴/多孔碳复合催化剂的制备及其电催化性能

采用离子交换法与热处理相结合的方法,以ZIF67为前驱体,硫代乙酰胺为硫源,制备出硫化钴/多孔碳(CoS/C)复合催化材料,并探讨了硫化时间对复合催化剂的形貌、结构及其氧还原(ORR)性能的影响。采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射仪(XRD)、N2吸附-脱附测定仪、X射线光电子能谱分析(XPS)、拉曼光谱仪(Raman)和旋转圆盘电极(RDE)技术表征催化剂的物理特征和电催化性能。研究结果显示,在碱性条件下该复合催化剂具有与20%(w/w)的商业Pt/C催化剂相媲美的ORR活性,其半波电位仅比Pt/C催化剂低31 mV。随着硫化时间的增加,硫化钴颗粒逐渐增大,催化剂中碳材料的无序程度出现先减小后增大的趋势。在硫化时间为10 min时,复合催化剂在0.1 mol·L-1KOH中表现出良好的电催化活性,且在ORR过程中复合催化剂的平均转移电子数可达到3.72,接近于4,说明氧气在该催化剂表面发生的是四电子转移过程。