Co/Co9S8/ZnO核壳结构纳米微球的制备与表征

在无水无氧条件下通过热分解还原制备Co纳米微粒,利用Co9S8和ZnO晶格的相匹配性,通过层层自组装对Co表面进行修饰,得到Co/Co9S8/ZnO核壳结构纳米微球.采用XRD、TEM、SQUID、光致发光光谱（PL）等对产物进行了表征.通过调节反应参数制备出核壳结构的Co/Co9S8/ZnO复合纳米微球,平均粒径58.8nm,壳层厚度均匀,常温下显示铁磁性,矫顽力为18.7kA/m.PL表明,产物在380~390nm处的带边跃迁不明显,光致发光最强峰在468nm处,属氧缺陷发射峰,研究了影响产物形貌的主要因素.结果表明,以油酸（OLA）及三正辛基氧化磷（TOPO）为溶剂和表面活性剂,Zn（acac）2温度为70℃、用量为1mmol,控制Co的硫化反应时间为5min,有利于核壳结构产物的形成.初步分析了Co/Co9S8/ZnO核壳结构纳米微球的形成机理.

MoS2@Co9S8蛋黄壳复合材料的制备及其电化学性能

近年来,过渡金属硫化物已成为锂离子电池理想的负极材料之一。其中,MoS_2具有的独特二维层状结构使得其能够让Li+在电化学反应中可逆地嵌入和脱出,且拥有较高的理论储锂容量(670 m A·h/g)而受到广泛关注。但MoS_2作为典型的半导体材料,电导率低下且在锂离子嵌入-脱出的过程中会发生较大程度的体积收缩膨胀,所以具有较差的倍率性能和循环性能,限制了其商业化的使用。很多研究通过优化MoS_2结构或与其它导电材料复合来克服上述缺陷。Co_9S_8具有较高的电导率,但由于其迟缓的离子传输动力学表现出低的首次库仑效率及较差的循环稳定性,基于此,将MoS_2与Co_9S_8结合利用二者协同效应来提高复合材料的电化学性能。本文采用溶剂热与气相沉积法制备得MoS_2@Co_9S_8蛋黄结构复合材料电极。MoS_2与Co_9S_8均匀分布于整个蛋黄壳结构,这有利于电子和锂离子的快速传输,从而有效地提升了电极的循环性能和倍率性能。其次,蛋黄壳的空穴有效缓解了在充放电过程中的体积膨胀,及其活性位点有效缩短了离子和电子的传输距离,提高了电极反应动力学并获得高比容量。MoS_2@Co_9S_8蛋黄壳复合物的循环性能与倍率性能在同等条件下均高于Co_9S_8和MoS_2,在电流密度为0.2 A/g下循环500圈后,放电容量仍能维持在631.5 m A·h/g。

Zn掺杂Co9S8纳米材料的制备及其在超级电容器和电催化析氢中的应用

采用原位溶剂热生长法设计合成了锌掺杂Co9S8纳米颗粒。各种表征技术和性能测试结果表明:锌掺杂Co9S8纳米颗粒的孔尺寸为18 nm,比表面积为23 m^2·g^-1;同时微量的锌掺杂显著增强了Co9S8的电催化析氢(HER)活性及电容器性能。在HER性能测试中,当电流密度为10 mA·cm^-2时电位为-361 mV,电流密度最高可达38.26 mA·cm^-2,且具有优异的循环稳定性。同时在电容器性能测试中具有较高的比电容,当电流密度为1 A·g^-1时,质量比电容和面积比电容分别为235.48 F·g^-1和812.4 mF·cm^-2。

片状Co9S8/ZnS/C复合材料的制备及电催化产氧性能

以六水合硝酸钴[Co(NO3)2·6H2O]为钴源、六水合硝酸锌[Zn(NO3)2·6H2O]为锌源、2,2′-硫代二乙酸(C4H6O4S)为硫源,采用溶剂热法制备出了片状的Co9S8/ZnS/C复合材料。采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)和N2吸附/脱附测试等手段对于片状Co9S8/ZnS/C复合材料结构和形貌等进行表征,同时对片状Co9S8/ZnS/C复合材料进行了电催化产氧性能测试。结果表明:片状Co9S8/ZnS/C复合材料的起始过电位为390 mV,塔菲尔斜率为144 mV·dec^-1,具有高的电催化产氧性能。

共沉淀法制备Co9S8/C材料以及性能研究

氢能作为新能源在未来的能源发展中发挥至关重要的作用。电解水制氢包括析氢和析氧两个半反应,具有低成本、无污染、储量丰富等优点,而析氧反应是电解水制氢中的决速步骤。介绍了一种简单的共沉淀方法,将碳材料复合到Co9S8催化材料上,并对其析氧性能进行了表征。对比没有碳材料复合的Co9S8,少量碳材料复合可以明显提高Co9S8的电解水析氧性能。通过X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、极化曲线、计时电流以及交流阻抗等技术对材料进行结构、形貌表征及电化学性能测试。结果表明,制备的Co9S8/C材料无杂相,在电流密度为10 mA/cm^2时,过电势为350 mV,塔菲尔斜率为102 mV/dec,具有高的电催化产氧性能。

MOF-derived Co9S8/MoS2 embedded in tri-doped carbon hybrids for efficient electrocatalytic hydrogen evolution

Metal-organic framework(MOF)derived hybrid materials have been developed as an efficient non-noblemetal electrocatalysts for clean energy conversion systems.In this work,a Co-based MOF containing nitrogen and oxygen heteroatoms(Co-NOMOF)mixed with the thiomolybdate[Mo3S(13)]^2- nanoclusters was used to prepare the N,S,O-doped carbon encapsulating Co9S8 and MoS2(Co9S8/MoS2@NSOC)nanocomposite by one-step pyrolysis.The Co9S8/MoS2@NSOC nanocomposite exhibited remarkable catalytic performance for hydrogen evolution reaction(HER)with overpotential of 194 and 233 mV in 1 M KOH and 0.5 M H2SO4 solution under 10 mA cm^-2,respectively,which was ascribed to the multiheteroatom-doped hierarchical porous carbon matrix and the synergistic effect of intrinsic activity of Co9S8 and MoS2.This work provides new opportunity for developing highly efficient non-precious metal electrochemical catalysts.

Co9S8-CuS纳米片阵列的电沉积制备及其电催化产氧性能研究

过渡金属硫化物因其制备简单、导电性好以及具有丰富的氧化还原性质被广泛用作电催化剂。在导电基底上原位生长复合材料被认为可有效提高催化剂的电催化性能。基于此,利用简单、可控的电沉积法,以泡沫铜作为导电基底,以硝酸铜和硝酸钴作为铜源和钴源原位制备了Co9S8-Cu S纳米片阵列。在三电极体系中,将Co9S8-Cu S纳米片阵列作为阳极在1 mol/L KOH溶液中得到了优异的电催化析氧性能,Co9S8-Cu S纳米片阵列获取50 m A/cm2电流密度所需的过电位仅为370 m V,其Tafel斜率低至108 m V/dec,其优异的电催化析氧性能归因于较大的催化活性面积以及复合材料中Co9S8与Cu S之间的协同作用。

Three-dimensionally interconnected Co9S8/MWCNTs composite cathode host for lithium–sulfur batteries

Several challenging issues,such as the poor conductivity of sulfur,shuttle effects,large volume change of cathode,and the dendritic lithium in anode,have led to the low utilization of sulfur and hampered the commercialization of lithium–sulfur batteries.In this study,a novel three-dimensionally interconnected network structure comprising Co9 S8 and multiwalled carbon nanotubes(MWCNTs)was synthesized by a solvothermal route and used as the sulfur host.The assembled batteries delivered a specific capacity of1154 m Ah g-1 at 0.1 C,and the retention was 64%after 400 cycles at 0.5 C.The polar and catalytic Co9 S8 nanoparticles have a strong adsorbent effect for polysulfide,which can effectively reduce the shuttling effect.Meanwhile,the three-dimensionally interconnected CNT networks improve the overall conductivity and increase the contact with the electrolyte,thus enhancing the transport of electrons and Li ions.Polysulfide adsorption is greatly increased with the synergistic effect of polar Co9 S8 and MWCNTs in the three-dimensionally interconnected composites,which contributes to their promising performance for the lithium–sulfur batteries.

Catalytic Co9S8 decorated carbon nanoboxes as efficient cathode host for long-life lithium-sulfur batteries

Lithium sulfur(Li-S)batteries with high specific capacity and energy density can bring enormous opportunities for the nextgeneration energy storage systems.However,the severe dissolution and shuttle effect of lithium polysulfides(LiPSs)is still the key issue that seriously impedes the development of practical Li-S batteries.Here,polar Co9S8 inlaid carbon nanoboxes(Co9S8@C NBs)have been investigated as cathode host for high-performance Li-S batteries.In this integrated structure,Co9S8 nanocrystals not only provide strong chemisorptive capability for polar LiPSs,but also act as a catalyst to accelerate polysulfide redox reactions;while carbon nanobox with large inner space can offer enough space to relieve the volume expansion and physically confine LiPSs’dissolution.As a result,the S/Co9S8@C NBs cathode exhibits high specific capacity at 1C and the capacity retention was^83%after 400 cycles,corresponding to an average decay rate of only^0.043%per cycle.

Sulfur-deficient Co9S8/Ni3S2 nanoflakes anchored on N-doped graphene nanotubes as high-performance electrode materials for asymmetric supercapacitors

In this paper,Co9S8/Ni3S2 nanoflakes(NFs)with sulfur deficiencies were grown in-situ on N-doped graphene nanotubes(NGNTs).They were successfully prepared through electrodeposition followed by hydrogenation treatment,which is able to act as a self-supported electrode for asymmetric supercapacitors(ASCs).Combining the defect-rich active materials with highly conductive skeletons,the hybrid electrode N-GNTs@sd-Co9S8/Ni3S2NFs show ultrahigh specific capacity of^304 mA hg^-1 and prominent rate capability(capacity retention ratio of^85%even at 100 Ag^-1),and deliver a long cycling lifespan of^1.9%capacitance loss after 10000 cycles.In addition,an ASC was constructed using the as-synthesized composite electrode as the positive electrode and active carbon(AC)as the negative electrode.The fabricated device shows a high energy density of^45.1 Wh kg^-1 at^3.4 kW kg^-1 and superior cycling stability.This work substantiates a smart strategy to fabricate novel composite electrode materials for next-generation supercapacitors by incorporating riched deficiencies into nanostructures.

Co_9S_8纳米晶聚集体的水热合成及其光谱研究

以七水合硫酸亚钴(CoSO4.7H2O)和无水亚硫酸钠(Na2SO3)为主要原料,以水合肼(N2H4.H2O)为还原剂,利用水热法合成了Co9S8纳米晶聚集体。运用X射线衍射(XRD)、场发射扫描电镜(FE-SEM)和透射电镜(TEM)对产物进行了表征,并利用傅里叶变换红外光谱仪(FTIR)对产物的红外光谱进行了测定和初步分析。实验结果表明,产物主要为Co9S8纳米晶聚集体,其中含有平均粒度约为2.5 nm Co9S8晶粒。聚集体的形貌呈六角片状,其平均直径约为2.1μm,厚度约为200 nm。

Co_9S_8单晶片水热还原合成与磁性(英文)

以七水合硫酸亚钴 (CoSO4·7H2 O)和无水亚硫酸钠 (Na2 SO3)为原料 ,水合肼 (N2 H4·H2 O)为还原剂 ,在180℃水热处理 72h ,成功地合成了片状Co9S8单晶 .产物分别用X射线粉末衍射 (XRD)、透射电子显微镜 (TEM)和振动样品磁强计 (VSM )表征 .实验结果表明 ,产物主要由直径为 0 .8～ 1.5μm的片状Co9S8单晶组成 ,在室温下具有铁磁性 ,其饱和磁化率 (Ms)和矫顽力 (Hc)分别为 65emu/g和 3 3

超声喷雾热解法制备Co_9S_8纳米球壳

以CoCl2.6H2O和硫脲CS(NH2)2为前驱物,利用超声喷雾热解法在300℃玻璃衬底上制备了Co9S8的纳米球壳.运用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)对产物进行了物相和形貌分析,结果表明:产物为直径约500 nm,形状相似但不规则的Co9S8球壳.同时,对其生长机理进行了初步研究.

大尺度Co_9S_8纳米线超声喷雾热解制备

以CoC l2.6H2O和CS(NH2)2为先驱物,运用超声喷雾热解法在300℃的玻璃衬底上成功地制备了Co9S8纳米线,所得Co9S8纳米线的直径约为500 nm.利用X射线衍射(XRD)、光学显微镜分别对产物的物相和形貌进行了表征,同时讨论了产生大尺度纳米线的软模板机理.

TiO_2包覆Co_9S_8的制备及其电化学储氢性能

目前,寻找新型能源成为解决能源和环境问题的关键,氢能以其高效能、无污染等优点成为研究重点。其中,开发具有高储氢量和优异循环稳定性的新材料是利用氢能的重要研究方向。近些年,Co_9S_8凭借其优良的电化学储氢性能和较高的储氢容量成为目前研究热点,但其抗粉化性能仍有待于进一步提高。本文采用溶胶凝胶法和煅烧法得到了不同质量分数TiO_2包覆Co_9S_8的电极材料,利用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)和电化学测试系统分析包覆材料组成与性能,研究不同质量分数的TiO_2对材料电化学储氢性能的影响。结果表明,当TiO_2质量分数为3%时,产物的储氢性能和循环稳定性最好,最大储氢容量(质量分数)为2.03%,且经过30次充放电后,其放电容量仍能保持在60%。

纳米杆状Co_9S_8的原位制备及其染料敏化电池对电极性能研究

寻找无铂、无FTO、导电性好且电催化性能优异的对电极对染料敏化电池的研究具有重大意义。本工作采用溶胶凝胶退火工艺在石墨纸基底上制备了Co_9S_8纳米杆,并用作染料敏化太阳能电池对电极。通过扫描电子显微镜、X射线衍射、透射电镜、循环伏安曲线、电化学阻抗谱、Tafel极化曲线以及光伏特性曲线分别对其形貌、物相、电催化活性及稳定性、光伏性能等进行研究。分析结果表明在柔性石墨纸上滴涂两次前驱体之后退火的样品表面生长有更为密集的Co_9S_8纳米杆,并且该样品具有良好的电催化活性以及优良的稳定性,与Pt电极相比(6.75%),其组装的电池具有更优异的光电转换效率(7.28%)。

一步水热法制备高效析氧3D花球阵列Co_(9)S_(8)/MoS_(2)@TM催化电极

以四水合钼酸铵、六水合硝酸钴和硫脲为原料,采用一步水热法在钛网(TM)上原位构筑了不同阵列结构Co_(9)S_(8)/MoS_(2)@TM催化电极。通过改变原料中钴、钼、硫的物质的量之比来调控Co_(9)S_(8)/MoS_(2)@TM电极的结构。采用SEM、XRD和XPS对Co_(9)S_(8)/MoS_(2)@TM进行物相分析和形貌表征,并在1 mol/L KOH电解液中对Co_(9)S_(8)/MoS_(2)@TM的电催化析氧性能进行了研究。结果表明,钴、钼、硫的物质的量之比为10∶14∶600时,制备的Co_(9)S_(8)/MoS_(2)@TM为3D花瓣状阵列结构,且在10 m A/cm^(2)电流密度下过电势为271 m V,塔菲尔斜率为88.5 m V/dec,具有良好的析氧稳定性和耐久性,展现了优异的电化学性能。

水热电沉积法生长Co_9S_8薄膜电极

采用水热电沉积法在泡沫镍基体上原位沉积Co_9S_8薄膜,并对其形貌、组成、结构和电化学性能进行表征和测试。结果表明,镍基Co_9S_8薄膜呈花瓣片状,并具有优异的电化学性能,其在电流密度为10mA/cm^2时,比电容可高达2538.7 F/g。即使电流密度扩大至50 mA/cm^2时,比电容依然可达1930.7 F/g。经过1000次循环(电流密度为20 mA/cm2),比电容仍可达为1825.2 F/g,电容保有率72.8%,经过1500次循环后,电容保有率61.4%。

Co_9S_8 nanowires@NiCo LDH nanosheets arrays on nickel foams towards efficient overall water splitting

Water electrolysis is considered to be an effective way to fabricate hydrogen, and it is desirable to find the highly efficient, inexpensive and good durability bifunctional electrocatalysts for overall water splitting.In this paper, we synthesis a unique structured catalyst that was composed by Co_9S_8 nanowires and nickel cobalt layered double hydroxide(NiCo-LDH) nanosheets. The ultrathin nanosheets decorated on the Co_9S_8 nanoarrays offer large specific surface area, numerous active edge sites and excellent electrical conductivity for fast electron transfer. Benefiting from this heterogeneous structure, the catalyst presents excellent catalytic performance in alkaline media. It requires 168 mV to reach current density of 10 mA/cm^2 for HER and 278 m V to reach current density of 30 mA/cm^2 for OER. When used as electrode in a homemade two-electrode system, it only needs t a voltage of 1.63 V to achieve current densities of 10 mA/cm^2, which proves Co_9S_8@NiCo LDH/NF as a superior bifunctional catalyst for water splitting.

Multi-scale regulation in S,N co-incorporated carbon encapsulated Fe-doped CO_(9)S_(8) achieving efficient water oxidation with low overpotential

Sulfide compounds provide a type of promising alternative for oxygen evolution reaction(OER)electrocatalysts due to their diversity,intrinsic activities,low-price and earth-abundance.However,the unsmooth mass transport channel,the collapse of the structure and insufficient intrinsic activities limit their potential for OER performance.In respond,the dense Fe-doped Co_(9)S_(8) nanoparticles encapsulated by S,N co-incorporated carbon nanosheets(Fe-Co_(9)S_(8)@SNC)were proposed and synthesized via fast thermal treatment from ultrathin metal-organic frameworks(MOFs)nanosheets.In designed catalysts,the nanosheet configuration connected by nanoparticles retained rich access for permeation of electrolyte and precipitation of O_(2) bubbles during OER process.Meanwhile,the outer carbon layer of Co9S8 provided additional catalytic activity while acting as armor to keep the structure stability.At the atomic scale,the doped Fe regulated the local charge density and the d-band center for facilitating desorption of oxygen intermediates.Benefiting from this multi-scale regulation strategy,the Fe-Co_(9)S_(8)@SNC displays an ultralow overpotential of 273 mV at 10 mA·cm^(-2) and small Tafel slope of 55.8 mV·dec^(-1),which is even close to the benchmark RuO_(2) catalyst.This concept could provide valuable insights into the design of other catalysts for OER and beyond.