Graphene Composites with Cobalt Sulfide: Efficient Trifunctional Electrocatalysts for Oxygen Reversible Catalysis and Hydrogen Production in the Same Electrolyte

Nitrogen and sulfur‐codoped graphene composites with Co₉S₈ (NS/rGO‐Co) are synthesized by facile thermal annealing of graphene oxides with cobalt nitrate and thiourea in an ammonium atmosphere. Significantly, in 0.1 m KOH aqueous solution the best sample exhibits an oxygen evolution reaction (OER) activity that is superior to that of benchmark RuO₂ catalysts, an oxygen reduction reaction (ORR) activity that is comparable to that of commercial Pt/C, and an overpotential of only ?0.193 V to reach 10 mA cm^?2 for hydrogen evolution reaction (HER). With this single catalyst for oxygen reversible electrocatalysis, a potential difference of only 0.700 V is observed in 0.1 m KOH solution between the half‐wave potential in ORR and the potential to reach 10 mA cm^?2 in OER; in addition, an overpotential of only 450 mV is needed to reach 10 mA cm^?2 for full water splitting in the same electrolyte. The present trifunctional catalytic activities are markedly better than leading results reported in recent literature, where the remarkable trifunctional activity is attributed to the synergetic effects between N,S‐codoped rGO, and Co₉S₈ nanoparticles. These results highlight the significance of deliberate structural engineering in the preparation of multifunctional electrocatalysts for versatile electrochemical reactions.     

Defect‐Laden MoSe2 Quantum Dots Made by Turbulent Shear Mixing as Enhanced Electrocatalysts

A high density of edge sites and other defects can significantly improve the catalytic activity of layered 2D materials. Herein, this study demonstrates a novel top‐down strategy to maximize catalytic edge sites of MoSe₂ by breaking up bulk MoSe₂ into quantum dots (QDs) via “turbulent shear mixing” (TSM). The ultrasmall size of the MoSe₂ QDs provides a high fraction of atoms in reactive edge sites, thus significantly improving the catalytic activities. The violent TSM further introduces abundant defects as additional active sites for electrocatalytic reactions. These edge‐proliferated and defect‐laden MoSe₂ QDs are found to be efficient electrocatalysts for the hydrogen evolution reaction, and useful as counter electrodes in dye‐sensitized solar cells. The work provides a new paradigm for creating edge‐proliferated and defect‐rich QDs from bulk layered materials.     

Design of active and stable oxygen reduction reaction catalysts by embedding Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> nanoparticles into nitrogen-doped carbon

The oxygen reduction reaction (ORR) is essential in research pertaining to life science and energy. In applications, platinum-based catalysts give ideal reactivity, but, in practice, are often subject to high costs and poor stability. Some cost-efficient transition metal oxides have exhibited excellent ORR reactivity, but the stability and durability of such alternative catalyst materials pose serious challenges. Here, we present a facile method to fabricate uniform Co _x O _y nanoparticles and embed them into N-doped carbon, which results in a composite of extraordinary stability and durability, while maintaining its high reactivity. The half-wave potential shows a negative shift of only 21 mV after 10,000 cycles, only one third of that observed for Pt/C (63 mV). Furthermore, after 100,000 s testing at a constant potential, the current decreases by only 17%, significantly less than for Pt/C (35%). The exceptional stability and durability results from the system architecture, which comprises a thin carbon shell that prevents agglomeration of the Co _x O _y nanoparticles and their detaching from the substrate.

Open image in new window

     

Template-directed synthesis of nitrogen- and sulfur-codoped carbon nanowire aerogels with enhanced electrocatalytic performance for oxygen reduction

Heteroatom doping,precise composition control,and rational morphology design are efficient strategies for producing novel nanocatalysts for the oxygen reduction reaction (ORR) in fuel cells.Herein,a cost-effective approach to synthesize nitrogen-and sulfur-codoped carbon nanowire aerogels using a hard templating method is proposed.The aerogels prepared using a combination of hydrothermal treatment and carbonization exhibit good catalytic activity for the ORR in alkaline solution.At the optimal annealing temperature and mass ratio between the nitrogen and sulfur precursors,the resultant aerogels show comparable electrocatalytic activity to that of a commercial Pt/C catalyst for the ORR.Importantly,the optimized catalyst shows much better long-term stability and satisfactory tolerance for the methanol crossover effect.These codoped aerogels are expected to have potential applications in fuel cells.     

氢氧化铝/膦掺杂丙烯酸树脂的热稳定性和协同阻燃效应

采用9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)与甲基丙烯酸-β-羟乙酯反应得到膦化物2-甲基-3-(6-氧代-6H-二苯并[c,e][1,2]氧磷杂己环-6-基)丙酸2-羟乙酯(DOPO-HM),将氢氧化铝(Alu)与DOPO-HM掺杂到丙烯酸树脂(AR)制备丙烯酸树脂阻燃复合材料AR/DOPO-HM/Alu。通过热重分析、极限氧指数(LOI)、扫描电镜、X射线光电子能谱(XPS)对复合材料及炭层进行分析。研究表明,DOPO-HM/Alu体系能协同提高复合材料的热稳定性和LOI,复合材料在空气和氮气中热分解炭层致密。XPS研究阻燃机理揭示DOPO-HM的分解产物聚磷酸催化分解基体成炭过程在Al2O3表面进行,焦磷酸铝的生成证明存在协同阻燃效应。Horowitz-Metzger理论计算复合材料的分解活化能,结果表明Al2O3对膦催化复合材料分解成炭过程具有正向助催化作用,协同提高复合材料阻燃效力。     

聚砜酰胺基单聚合物复合材料的热性能及降解动力学

采用热重分析对作为耐高温材料使用的聚砜酰胺基单聚合物复合材料(PSA SPCs)进行热性能研究。通过计算积分程序分解温度(IPDT)和温度指数Ts分别评价材料的热稳定性和长期使用温度,通过计算温度指数Tzg来表征耐热性能。PSA SPCs的IPDT、Ts以及Tzg分别为1305℃,248℃和255℃,而PSA树脂材料相对应的参数值依次是1162℃,243℃和244℃,表明PSA SPCs的热性能优于PSA树脂材料。采用不同升温速率,分别用Flynn-Wall-Ozawa法和Kissenger法研究其热降解动力学,计算得到反应活化能(Ea)分别为152.26 k J/mol,146.85 k J/mol,优于PSA树脂材料的Ea值(133.54 k J/mol,127.88 k J/mol)。     

含磷腈环氧树脂阻燃和热解动力学

采用热重(TG)和微商热重(DTG)实验分析技术,分别对自制的六-对氨基苯氧基环三磷腈(PNH)和4,4’-二氨基二苯甲烷(DMA)为E51型环氧树脂的固化剂,研究了在氮气和空气氛围中2种环氧树脂的阻燃特性和热解动力学;运用Achar法和Coats-Redfern法建立了二者的热裂解动力学模型,得到了2种体系的动力学表观活化能和指前因子。研究表明,与不含磷环氧树脂相比,磷腈固化的环氧树脂更易发生热裂解,而在高温阶段却明显具有阻燃特性;磷腈固化的环氧树脂裂解后期残炭量较高,其活化能与其阻燃机理有关:即表观活化能越大阻燃性越强。     

ZrSi_2/硼酚醛泡沫的制备及其裂解产物的增强机制

以ZrSi_2颗粒填充硼酚醛树脂制备了一种耐高温且裂解后结构较为完整的泡沫复合材料。研究了ZrSi_2颗粒质量分数对泡沫复合材料固化机制、高温裂解行为及裂解前后压缩性能的影响,并分析了ZrSi_2颗粒对泡沫复合材料裂解产物的增强机制。结果表明:添加的ZrSi_2颗粒虽未参与硼酚醛树脂的固化交联,但会和硼酚醛树脂裂解放出的气体挥发物发生化学反应,提高了裂解产物的残炭率和压缩比强度。当添加的ZrSi_2颗粒质量为硼酚醛树脂质量的10%时,裂解产物的残炭率和压缩比强度提高最为显著。ZrSi_2/硼酚醛泡沫经过裂解后,ZrSi_2颗粒作为第二相粒子钉扎在裂解产物的孔壁上,化学反应使得部分裂解气体挥发物被吸收并转化为固相产物,明显减少的缺陷提高了裂解产物的力学性能。     

纳米TiO_2/PC-PP光扩散复合材料的结构与性能

采用熔融复合的方法制备了纳米TiO_2/聚碳酸酯-聚丙烯(TiO_2/PC-PP)光扩散复合材料。分别采用SEM和DSC研究了纳米TiO_2/PC-PP复合材料的微观结构和等温结晶性能,并研究了复合材料的热稳定性与光学性能。结果表明:纳米TiO_2的加入使得光扩散体系中分散相的平均尺寸变小,形态更加均一,并且随着复合材料中纳米TiO_2质量分数的增加,复合材料的半结晶时间逐渐延长,总体结晶速率变慢。纳米TiO_2的加入使复合材料的初始热降解温度以及最终残余量升高,当PP中纳米TiO_2质量分数为5%时,复合材料的透光率达到80%,雾度为88%,此时纳米TiO_2/PC-PP复合材料的光扩散性能较好。