氮掺杂再生活性炭的制备及电催化氧还原反应性能研究

为解决危废活性炭传统回收方式带来的资源浪费和环境污染等问题,本工作以抗生素脱色废活性炭为原料、氨气为氮源,采用高温热解再生法将氮元素通过sp²杂化键合进入到活性炭骨架中,制备了氮掺杂再生废活性炭氧还原反应(ORR)催化剂,分析了氮掺杂再生活性炭的物相组成、微观形貌、电化学性能。结果表明,当温度为1 000℃、退火时间为1 h时,所制备的N-RWAC-1000-1氧还原电催化性能最佳。N-RWAC-1000-1具有丰富的微孔和介孔结构,比表面积可达908 m²/g,在碱性介质中的起始电位为0.92 V(vs.RHE),半波电位为0.82 V(vs.RHE),均接近商业20%(质量分数)的铂碳催化剂。此外,氮掺杂再生炭拥有优于商业化铂碳的循环稳定性和甲醇耐受性,有望成为新的氧还原催化剂以期为抗生素脱色废活性炭的高值化利用提供了新的方向。     

掺磷非晶氧化钛负载铂用于高效催化氧化挥发性有机化合物

高活性催化剂是挥发性有机化合物(VOCs)催化氧化消除的关键因素。本研究通过简单的共沉淀法成功制备了具有高比表面积的非晶介孔磷掺杂氧化钛负载铂催化剂(Pt/ATO-P)。通过P掺杂, 既可获得非晶介孔结构, 又可获得高ATO-P比表面积(可达278.9 m²·g^-1)。非晶介孔Pt/ATO-P催化剂显示出优异的VOCs催化氧化性能和良好的热稳定性。Pt/ATO-P样品在空速为36000 mL·h^-1·g^-1、甲苯浓度为10000 mL·m^-3的反应条件下, 对甲苯催化氧化的T₅₀和T₉₀(实现50%和90%转化率所需的温度)分别为130 ℃和140 ℃, 明显优于无磷催化剂Pt/TiO₂。这些发现可以为拓展非晶介孔磷化材料在环境净化和能源转化等领域的应用提供重要参考。     

沉积时间对聚醚醚酮表面类金刚石薄膜的结构和性能的影响

采用直流磁控溅射技术在聚醚醚酮(PEEK)表面制备不同厚度的类金刚石(DLC)薄膜,研究了沉积时间对其表/界面结构、组分、疏水、力学和光透过性能的影响。结果表明,在平均沉积速率为5.71 nm/min的条件下,随着沉积时间的延长DLC薄膜的厚度线性增大、碳原子的致密性提高、界面互锁结构增强,而界面结合强度逐渐降低。沉积时间≤15 min时,基体结构的影响使拟合计算出的I_D/I_G值为0.23~0.25和sp²/sp³比值较小(0.58~0.74);沉积时间>15 min时基体的影响较小,I_D/I_G值突增大至0.81,sp²/sp³值也比较大(0.96~1.12)。沉积时间的延长使PEEK基体的温度逐渐升高,使膜内的sp²/sp³值逐渐增大。薄膜表面的氧含量先降低然后趋于平缓,部分C=O转化为C-O。随着沉积时间的延长,PEEK/DLC复合薄膜的硬度、弹性模量及防紫外线和阻隔红外线性能都逐渐提高,其表面粗糙度和疏水性的变化趋势是先提高后降低。沉积时间为32 min的薄膜,其表面粗糙度和水接触角达到最大值,分别为495 nm和108.29°。     

Zn2+掺杂诱导Eu3+激活BiOCl层状半导体的反常发光性能研究

采用固相法在500℃下成功制备Zn²⁺掺杂BiOCl:Eu³⁺层状半导体, 并研究了Zn²⁺ (0~20mol%)掺杂对Eu³⁺激活BiOCl层状半导体发光性能的影响。利用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)、傅里叶变换红外光谱(FT-IR)、激发-发射光谱、荧光寿命衰减曲线对样品的结构和性能进行表征。研究发现, 随Zn²⁺掺杂浓度增大, BiOCl晶体结构不变, Eu³⁺荧光寿命延长, 但发光强度却出现先减后增的反常现象。综合分析表明这可能与BiOCl特殊的层状结构有关。通过XRD和XPS的表征可以推断: 当Zn²⁺掺杂浓度≤10mol%, Zn²⁺在BiOCl中掺杂方式以晶胞层间隙掺杂为主; 当Zn²⁺掺杂浓度>10mol%后, 掺杂方式逐渐向取代掺杂转变。两种掺杂机制对Eu³⁺荧光寿命的改变以及形成缺陷对基质能量传递效率的影响可能是形成上述反常现象的主要原因。研究结果有助于认识稀土掺杂层状半导体的发光性能及影响规律, 并对Eu³⁺掺杂BiOCl这类新型发光材料的开发设计具有指导意义。     

碱性溶液中不同微观结构的Fe-N/C催化剂氧还原性能的稳定性对比研究

Fe-N/C催化剂在氧还原反应中的作用机理对于开发高效、可持续使用的非贵金属催化剂在聚合物电解质膜燃料电池中的应用至关重要, 但目前仍存在很多的难以攻克的问题。为了揭示纳米结构与电化学活性的关系, 本研究开发了一种具有高电化学活性的Fe-N/C氧还原催化剂, 该催化剂含有Fe-N_x位点和被氮掺杂的碳纳米管包裹的Fe/Fe₃C纳米晶体两种具有氧还原反应电化学活性的纳米结构。尽管不含贵金属铂, 本研究合成的Fe-N/C催化剂在碱性条件下仍显示出较高的ORR活性, 半波电势为0.86 V(vs RHE), 质量活性为18.84 A/g(0.77 V(vs RHE), 极限电流密度为-4.3 mA·cm ^-2。同时, 电子转移数为3.7(0.2 V(vs RHE), 说明Fe-N/C催化剂中4电子ORR反应的比例较高。石墨烯包覆的金属Fe/Fe₃C纳米晶生长N-CNTs后, 材料的导电性有所提高, 并且Fe-N_x活性位点在Fe/Fe₃C纳米颗粒表面分布均匀, 改善了材料的电化学活性。本研究为非贵金属氧还原电催化剂的继续深入研究以及广泛应用于商业化生产提供了一定的借鉴和依据。     

氢氧化钾活化制备可再生多孔碳及其电催化氧还原性能研究

氧还原反应缓慢的动力学过程严重限制了燃料电池的能量转换效率, 而商用Pt/C催化剂成本太高、资源稀缺、稳定性差, 需要寻找合适的材料来取代商用的Pt/C催化剂。近年来, 氮掺杂多孔碳材料因其独特的物理和化学特性吸引了大量的关注。本文使用富含氮元素的可再生土豆作为生物质前驱体, 通过简单的一步热解过程和KOH活化方法相结合制备出了一系列氮掺杂多孔碳电催化剂; 并系统研究了KOH用量和活化温度对碳基体孔结构和电催化性能的影响。结果表明, 当活化温度为750 ℃、KOH与碳的质量比为3/1时, 所制备的催化剂(NPC-750)的氧还原活性最高, 起始电位和半波电位分别达到0.89和0.79 V (vs. RHE), 极限电流密度达到5.53 mA?cm ^-2。NPC-750优异的氧还原催化活性主要归因于其发达的孔结构、高的比表面积(1134.2 m ²?g ^-1)和合适的氮含量(1.57at%)。同时, 优异的循环稳定性和抗甲醇中毒性能进一步说明这些生物多孔碳材料是潜在的低成本氧还原电催化剂。此外, 这些高比表面积多孔碳在超级电容、吸附/分离、催化以及电池等领域也具有潜在的应用前景。     

氮硫共掺杂碳材料均匀担载核壳纳米颗粒Co@Co9S8作为氧还原催化剂的研究

开发高效、稳定的非贵金属氧还原(ORR)催化剂是促进燃料电池商业化进程的关键。通过树脂衍生N、S共掺杂碳材料负载原位生成的Co@Co₉S₈核壳结构纳米颗粒，制备出一种具有良好活性和稳定的非贵金属催化剂Co@Co₉S₈/NSC。电化学测试结果表明：Co@Co₉S₈/NSC催化剂的半波电位(E_1/2)和极限电流密度可与商业Pt/C催化剂相媲美。同时相较商业Pt/C催化剂，其还具有极好的抗甲醇活性。此外，计时电流测试表明：持续老化10000s后，Co@Co₉S₈/NSC的电流密度保持了初始值的97.5%,远低于商业Pt/C催化剂的23.3%。为构建高活性高稳定性核壳结构ORR催化剂提供了新的思路，同时其思路也可以应用于其他新能源电极材料如Li-空气电池、Li-S电池及超级电容器等。     

原位负载Pt-Co高指数晶面催化剂的制备及其电催化性能

直接乙醇燃料电池(DEFC)具有燃料易得、绿色高效的优点,得到了广泛的研究,但是DEFC催化剂存在催化效率低、稳定性差的问题,制约了其快速发展。本研究采用液相水热合成法,以聚乙烯吡咯烷酮(PVP k-25)为分散剂和还原剂、甘氨酸为表面控制剂和共还原剂,通过调控Pt-Co金属前驱体的摩尔比,一步制备了XC-72R炭黑负载的Pt₁Co_x/C高指数晶面纳米催化剂,实现了催化剂晶粒在碳载体上的原位生长。Pt₁Co_1/3/C纳米催化剂暴露的高指数晶面主要包括(410)、(510)和(610)晶面。在晶体生长过程中, Pt₁Co_1/3/C纳米催化剂晶粒由“类球体”转变立方块,最终得到具有高指数晶面取向的内凹形貌。Pt₁Co_1/3/C高指数晶面纳米催化剂的电催化活性最高,其电化学活性表面积为18.46 m²/g,对乙醇氧化峰电流密度为48.70 mA/cm²,稳态电流密度为8.29...     

氮掺杂碳纳米片负载Fe-Co-Pt复合材料的制备及其氧还原电活性

制备高活性和高稳定性的电催化剂复合材料一直是燃料电池与金属-空气电池的重要研究内容.以双氰胺作为碳氮源,通过酞菁钴和二茂铁提供金属纳米颗粒,对其混合物进行简单的高温热解得到负载铁钴合金的氮掺杂碳纳米片(Fe1-Co1-N/C);最后利用沉积法将少量铂引入到Fe1-Co1-N/C上,得到负载铂铁钴三金属合金的氮掺杂碳纳米...     

镍基MOF衍生Ni@PC用于氧还原催化性能研究

开发高效、低成本的非贵金属氧还原催化剂是提高燃料电池效率的关键。以六水合硝酸镍和二甲基咪唑作为金属源和氮源，制备Ni-MOF前驱体，并采用低温热解法合成了纳米棒状镍掺杂多孔碳(Ni@PC)复合材料。通过扫描电子显微镜、X射线衍射仪、拉曼光谱和物理吸附仪等多种表征手段，对催化剂进行形貌和结构表征。利用旋转圆盘电极技术测试了其氧还原催化性能。结果表明：Ni@PC呈现三维交错的纳米棒状，其比表面积为178.7m²/g,具有介孔结构。在0.1mol/L KOH电解液中，Ni@PC的氧还原起始电位为0.89V(vs RHE),其极限电流密度可达4.91mA/cm²,在动力学电位区，Ni@PC的Tafel斜率为64mV/dec,氧气分子在Ni@PC催化剂上以四电子机理反应还原成水，该催化剂具有优异的耐久性和抗甲醇稳定性。因此，Ni@PC有望替代商业Pt/C催化剂，在能源领域具有广阔的应用前景。     

Low temperature internal friction of diamond-like carbon films

We have studied the internal friction of amorphous diamond-like carbon films prepared by pulsed-laser deposition from 0.4 to 300 K. The low temperature internal friction below 10 K is dominated by the atomic tunneling states for amorphous solids, which is a measure of structure disorder. We have tried to vary the content of sp³ carbon atoms versus sp² ones by changing laser fleunce, by doping with N and Ar, and by annealing at 500 °C for 20 min. Our results show that the internal friction varies about one order of magnitude from 2×10⁻⁵ to 2×10⁻⁴, and its value is higher with higher sp³ content when the film quality is generally considered superior. However, it is known that as-deposited diamond-like carbon films with high sp³ content are heavily stressed. Annealing and doping are used to release the stress. We conclude that in addition to tetrahedral bonding, low stress is also important in reducing structure disorder associated with the low energy tunneling states in amorphous solids.     

氮化碳在场发射冷阴极材料中的研究进展EI北大核心CSCD

氮化碳具有优良的热稳定性、高热导率、较大的禁带宽度和负的电子亲和势等优点,是一种极具潜力的场发射阴极材料。本文在介绍氮化碳的结构、性能以及作为场发射材料的研究现状的基础上,着重评述了氮化碳薄膜和粉体的制备方法;从优化结构中的sp^(2)簇的数量及尺寸、调控表面形貌、元素掺杂,以及通过与其他场发射材料复合或表面修饰形成多级发射结构等方面,阐述了优化氮化碳场发射性能的方法。最后总结了氮化碳薄膜和粉体分别作为场发射阴极材料仍然存在的问题,并以此指出将来开展相关研究的重点在于继续优化其场发射性能,以及探索其内部结构、缺陷等对场发射性能的影响。     

Photoelectron spectroscopy of ion-irradiated B-doped CVD diamond surfaces

Chemical vapour deposition (CVD) diamond films were irradiated by 1 keV argon ions at room temperature with doses ranging from 3.6 × 10¹² to 1.1 × 10¹⁶ Ar⁺ cm². The influence of sputtering on the valence band density of states of a boron-doped CVD diamond film was investigated by ultraviolet photoelectron spectroscopy and the changes in the plasmon features were observed by X-ray photoelectron spectroscopy of the carbon Is core level and its loss region. A gradual change from typical diamond features to amorphous carbon was observed after prolonged bombardment times. Above a critical dose D_crit of 5.8 × 10¹⁴ Ar⁺ cm² the damaged surface layer is characterized by a splitting of the C Is bulk peak into two components: a bulk-like diamond peak at 285.3 eV binding energy and a defect peak with 1 eV lower binding energy, which is attributed to the production of an amorphous sp²-rich carbon matrix. Moreover additional occupied states in the range of 0–4 eV binding energy, completely different to those observed on reconstructed diamond surfaces, were observed in the valence band spectra of the ion-irradiated diamond surface. These filled states can also be attributed to the amorphous carbon matrix which is formed at high doses. At very low doses (< 3 × 10¹⁴ ions cm²) only a band bending of the C Is diamond core level peak, along with the formation of some occupied states in the band structure at around 3.8 eV binding energy was observed. A comparison with annealed hydrogen-free CVD diamond surfaces shows some similarities concerning these filled states. The obtained spectra are compared with other crystalline and amorphous forms of carbon and the results are discussed in terms of an irradiation-induced change in the atomic structure of the surface. A comparison of ion bombarded and annealed diamond samples clearly shows that no graphitization takes place in the latter case.     

Electrical properties of reactively sputtered carbon nitride films

Carbon nitride films with β-C₃N₄ crystals of 200 nm grain size were grown on Si (1 0 0) substrates using magnetron sputtering. These films were characterized by transmission electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. Carbon nitride films had low surface roughness. Maximum N/C ratio of 0.5 was achieved in the films. Chemical bonds of sp, sp² and sp³ coexisted in the films. The fraction of each bond was related to the deposition conditions. The resistivities of the films were measured, which ranged from 1×10³ to 1×10⁷ Ω cm. The measured resistivity results indicated that the carbon nitride films had semiconductive properties. The resistivity largely depended on the sp³/sp² ratio. Effects of N₂ fraction, target current and substrate bias were investigated. All these deposition parameters had influence on the chemical bonds of the films, and on the resistivities too. High sp³/sp² ratio resulted in high resistivity.     

直接甲醇燃料电池电催化剂的研究及进展

从铂系和非铂系两个方面综述了近年来直接甲醇燃料电池电催化剂的研究及进展。     

Er2O3掺杂Gd2(Zr0.8Ti0.2)2O7陶瓷的物理性能

用固相反应法制备(Gd_1-xEr_x)₂(Zr_0.8Ti_0.2)₂O₇(摩尔分数x=0,0.2,0.4)陶瓷并测试其晶体结构、显微形貌和物理性能,研究了Er₂O₃掺杂的影响。结果表明,(Gd_1-xEr_x)₂(Zr_0.8Ti_0.2)₂O₇陶瓷具有立方烧绿石结构,显微结构致密,在室温至1200℃高温相的稳定性良好;Er³⁺掺杂降低了陶瓷材料的热导率和平均热膨胀系数,当x=0.2时,其1000℃的热导率最低(为1.26 W·m^-1·k^-1)。同时,Er³⁺掺杂还提高了这种材料的硬度和断裂韧性。     

Electrical characterization of CVD diamond thin films grown on silicon substrates

Diamond thin films grown on high resistivity, 100 oriented silicon substrates by the hot filament chemical vapor deposition (HFCVD) method have been characterized by four-point probe and current-voltage (through film) techniques. The resistivities of the as-grown, chemically etched and annealed samples lie in the range of 10² Ω cm to 10⁸ Ω cm. The Raman measurements on these samples indicate sp³ bonding with a sharp peak at 1332 cm⁻¹. The surface morphology as determined by scanning electron microscope shows polycrystalline films with (100) or (111) faceted structures with average grain size of ≈2.5 μm. The through film current-voltage characteristics obtained via indium contacts on these diamond films showed either rectifying or ohmic behavior. The difference in Schottky and ohmic behavior is explained on the basis of the high or low sheet resistivities measured by four-point probe technique. 5% methane to hydrogen concentration during film growth resulted in poor surface morphology, absence of sp³ bonds, and low resistivity.     

Characterization of ion-beam-deposited diamond-like carbon films

Diamond-like carbon (DLC) films are excellent prospects for a wide range of high-technology applications but their precise structure and properties are not well understood. The purpose of the present work was to use several complementary techniques to characterize the nature, structure and microstructure of DLC films. Thin DLC films were deposited on various substrates in the presence of a Si interlayer (500 Å thick) using CH₄ ion-beam deposition at an acceleration energy of 750 eV and a current density of about 2.5 mA cm⁻². The Si interlayer was deposited by either e-beam evaporation or Si evaporation enhanced by Ar⁺ beam bombardment (1 keV). The produced DLC films were featureless, very smooth and of high hardness (2900–3300 kg mm⁻²). Auger electron spectroscopy and electron diffraction showed that the films were mainly amorphous. Their microstracture was characterized by a three-dimensional network structure with a medium-range order of about 25 nm. Fourier transform infrared and Raman spectroscopies showed that the films were mainly composed of sp³ and sp² carbon-bonded hydrogen. The sp³/sp² ratio varied from 3.2 to 4.1 and was found to depend on the nature of the Si bond layer. The results showed that the nucleation of the diamondlike structure was promoted on the Si interlayer that was deposited under Ar⁺ beam bombardment. This effect can be explained by the higher surface roughness produced in this interlayer as suggested by the reflectivity measurements. Spectroscopic ellipsometry revealed that the films had an optical band gap between 1.56–1.64 eV. The present results are consistent with previous proposals suggesting that the DLC structure is composed of small graphitelike clusters (involving fused six-fold rings) that are interconnected by sp³-bonded carbon.     

面向金属-空气电池和中低温固体氧化物燃料电池应用的钴基电催化剂综述

在21世纪的今天,由石油、煤炭等化石资源的过度开发与使用所引发的能源和环境问题日趋严重,开发经济、高效的能源转换与存储装置已成为新时代的研究主题。金属-空气电池和中低温固体氧化物燃料电池,作为高效的能源转换与存储装置,可以实现化学能向电能的高效转换,具有效率高、环境友好、成本低的显著优点,在过去十几年内受到了研究者的广泛关注,取得了惊人的成果。但与此同时,人们在研究中发现阴极(正极)缓慢的氧还原和氧析出反应速率极大地降低了电池转换效率,增加了应用成本,在很大程度上制约了金属-空气电池和中低温固体氧化物燃料电池的商业化发展和应用。钴基催化剂作为一种高效阴极材料,相比贵金属成本较低,且具有混合离子-电子导电性,可以有效降低极化电阻,对阴极氧还原和氧析出反应显示出高催化活性,近年来吸引了国内外学者极大的研究兴趣。对于金属-空气电池,虽然钴基催化剂如钴氧化物、尖晶石型氧化物、钙钛矿型氧化物等材料能够显著地提高金属-空气电池的电容量和循环性能,并且降低充电电压,有效降低极化,但是其催化活性和稳定性有待提高,催化机理和活性位点也需要进一步明确和探究;对于中低温固体氧化物燃料电池,钴基催化剂包括La_(1-x)Sr_xCoO_3-δ、La_(1-x)Sr_xCo_(1-y)FeyO_3-δ、Ba_(1-x)Sr_xCo_yFe_(1-y)O_3-δ和钴基双钙钛矿等材料可以大大降低阴极极化电阻和面积比电阻,提高功率密度,但是相对其他催化剂,热膨胀系数普遍较高,稳定性也较差。为了进一步提高钴基催化剂应用在金属-空气电池和中低温固体氧化物燃料电池中的催化活性,研究者采用了掺杂其他金属元素、与其他物质组成复合阴极材料以及贵金属修饰等方法,在很大程度上提高了这两种电池的性能。本文简要介绍了金属-空气电池和中低温固体氧化物燃料电池的结构、工作原理,并在此基础上着重评述了近年来面向这两种能源转换与存储器件的,包括钴氧化物、钙钛矿型氧化物、尖晶石型氧化物和双钙钛矿氧化物等在内的各种钴基电催化剂的制取、改性和性能研究探索与成果。