薄层光谱电化学研究多巴胺在碳纤维电极上的氧化过程

本文用碳纤维制成光透电极,用电化学与紫外光谱联用技术研究了多巴胺在碳纤维电极上的电氧化,测定了式电位和反应的电子转移数,并求得了多巴胺的标准电极反应速率常数,由其紫外吸收的红移现象证明了多巴胺在电极上氧化的初级产物是醌式结构,本文同时发现了其氧化产物的后继反应,用单电位阶跃计时吸收法测定了后继反应的速率常数,并提出了可能的后续反应机理。     

无氧条件下Pd/CeO2催化剂表面NH3还原NO过程中N2O形成机理研究

氮氧化物(NO_x,主要包括NO和NO_2)是主要的大气污染物之一,造成酸雨,光化学烟雾和臭氧层破坏等环境问题,甚至直接危害人体健康.化石燃料燃烧和汽车尾气排放是NO_x的主要来源,严格控制火力发电厂,大型锅炉,汽车尾气等污染源中NO_x的排放刻不容缓.以NH_3为还原剂选择性催化还原NO_x(NH_3-SCR)是目前公认的最有效的NO_x脱除技术,然而在催化NO_x还原为N_2的过程中往往伴随着副产物N_2O的生成,降低了催化剂的选择性,造成温室气体效应和破坏臭氧层等环境问题.因此充分理解NH_3-SCR过程中N_2O的形成机理对于抑制N_2O的产生、提高催化剂的选择性十分重要.本文将高度分散的Pd纳米团簇负载在Ce O_2纳米棒上制成Pd/Ce O_2催化剂,结合NH_3-TPD, NO-TPD和原位傅里叶转换红外光谱等表征手段研究了无氧条件下该催化剂上利用NH_3催化还原NO过程中N_2O的产生路径.结果表明, N_2O的形成途径与反应温度和反应气体的浓度相关.当反应气体中NH_3含量大于化学计量比时,在反应温度低于200°C时,由NH_3活化产生的吸附态H·自由基与催化剂表面吸附的NO反应先生成中间产物HON,两个HON分子进一步反应生成N_2O;过量的吸附态的H·自由基也可以与HON反应生成N_2,所以低温下(200°C)随着反应气氛中NH_3的增加,解离生成的H·也随之增加,促进反应向着生成N_2的方向进行,从而抑制了N_2O的产生.随着反应温度增加, NH_3解离产生的H·被CeO_2表面的O捕获形成羟基,中间产物HON的生成被切断,从而阻断了N_2O的生成.同时由于体系中含有大量的NH_3,吸附态的NO会优先与活化态的NH_3物种反应生成N_2,阻碍了NO解离生成N_2O这一过程的发生,因此NH_3过量情况下在高温下观察不到N_2O的产生,可获得100%的N_2选择性.但是当反应气体中的NH_3含量不足时,即体系中含有过量的NO,当反应温度高于250°C, NO可在催化剂表面解离生成吸附态的N·自由基和O·自由基, N·自由基可进一步与吸附态的NO反应生成N_2O, NO的解离是N_2O生成的速控步,还原性吸附物种对O·自由基的捕捉将有利于N_2O的生成.当反应温度介于200–250°C, NH_3解离产生的H·自由基既可以与NO结合生成HON中间产物,又能被CeO_2表面的O捕获形成羟基,两个反应之间存在竞争,此时N_2O产生与反应气体浓度之间的关系不再呈单调变化.     

等离子体增强化学气相沉积法制备立方氮化硼薄膜过程中的表面生长机理

利用感应耦合等离子体增强化学气相沉积法以Ar，He，N₂和B₂H₆为反应气体制备了高纯立方氮化硼薄膜.用四极质谱仪对等离子体状况进行了系统的分析，发现B₂H₆完全被电离而N₂只是部分被电离.H₂和过量的N₂在等离子体中生成大量中性的H原子和活化的N^*₂，它们与表面的相互作用严重地阻碍了立方 关键词： 立方氮化硼薄膜 等离子体 质谱     

Influence of oxygen on the growth of cubic boron nitride thin films by plasma-enhanced chemical vapour deposition

Cubic boron nitride thin films were deposited on silicon substrates by low-pressure inductively coupled plasma-enhanced chemical vapour deposition. It was found that the introduction of O₂ into the deposition system suppresses both nucleation and growth of cubic boron nitride. At a B₂H₆ concentration of 2.5\% during film deposition, the critical O₂ concentration allowed for the nucleation of cubic boron nitride was found to be less than 1.4\%, while that for the growth of cubic boron nitride was higher than 2.1\%. Moreover, the infrared absorption peak observed at around 1230--1280~cm^-1, frequently detected for cubic boron nitride films prepared using non-ultrahigh vacuum systems, appears to be due to the absorption of boron oxide, a contaminant formed as a result of the oxygen impurity. Therefore, the existence of trace oxygen contamination in boron nitride films can be evaluated qualitatively by this infrared absorption peak.     

纳米碳管的电化学贮锂性能

用透射电镜、高分辩透射电镜、X射线衍射和拉曼光谱表征了用催化热解法制备的纳米碳管的结构,研究了纳米碳管的电化学嵌脱锂性能.以纳米级铁粉为催化剂热解乙炔气得到的纳米碳管石墨化程度较低,结构中存在褶皱的石墨层、乱层石墨和微孔等缺陷,具有较高的贮锂容量,初始容量为640mAh/g,但循环稳定性较差.而以纳米级氧化铁粉为催化剂热解乙烯得到的纳米碳管结构比较规则,循环稳定性较好,但贮锂容量较低,初始容量为282 mAh/g.讨论了纳米碳管的结构对其温度特性和不同电流密度下的充放电容量的影响.     

纳米碳管的分叉结构

应用催化剂热解碳氢气及热丝CVD两种不同的方法制备了含有分叉结构的纳米碳管,并用透射电镜考察了分叉碳管的形貌及微结构特征.结果表明：分叉结构的形态与制备方法有关,前者沿生长方向的呈规则节突状分布,而后者的分支碳管与未分支的形态类同.纳米碳管分叉结构的形成可能与制备条件的扰动有关,并因此改变其输运特性. 关键词：     

Residual compressive stress and intensity of infrared absorption of cubic BN films prepared by plasma enhanced chemical vapor deposition

Theoretical and experimental investigations on the dependence of the intensity of infrared （IR） absorption of poly- crystalline cubic boron nitride thin films under the residual compressive stress conditions have been performed. Our results indicate that the intensity of the IR absorption is proportional to the total degree of freedom of all the ions in the ordered regions. The reduction of interstitial Ar atom concentration, which causes the increase in the ordered regions of cubic boron nitride （cBN） crystallites, could be one cause for the increase in the intensity of IR absorption after residual compressive stress relaxation. Theoretical derivation is in good agreement with the experimental results concerning the IR absorption intensity and the Ar interstitial atom concentration in cubic boron nitride films measured by energy dispersion X-ray spec- troscopy. Our results also suggest that the interstitial Ar is the origin of residual compressive stress accumulation in plasma enhanced cBN film deposition.     

立方氮化硼薄膜的最新研究进展

立方氮化硼(cBN)作为一种在自然界中并不存在的人造材料具有优异的理化特性. 在超硬刀具、高温电子器件和光学保护膜等领域有着广泛的应用前景,已经成为材料科学的研究热点之一. 但是气相生长高质量cBN薄膜仍然还有许多难点需要攻克. 在综述近几年cBN薄膜研究所取得的一些突破性进展后,结合研究现状提出今后可能的主要研究方向. 关键词： 立方氮化硼薄膜 压缩应力 异质外延 掺杂     

In situ infrared spectroscopic study of cubicboron nitride thin film delamination

This paper investigates the procedure of cubic boron nitride （cBN） thin film delamination by Fourier-transform infrared （IR） spectroscopy. It finds that the apparent IR absorption peak area near 1380cm^-1 and 1073 cm^-1 attributed to the B-N stretching vibration of sp2-bonded BN and the transverse optical phonon of cBN, respectively, increased up to 195% and 175% of the original peak area after film delamination induced compressive stress relaxation. The increase of IR absorption of sp2-bonded BN is found to be non-linear and hysteretic to film delamination, which suggests that the relaxation of the turbostratic BN （tBN） layer from the compressed condition is also hysteretic to film delamination. Moreover, cross-sectional transmission electron microscopic observations revealed that cBN film delamination is possible from near the aBN（amorphous BN）/tBN interface at least for films prepared by plasma-enhanced chemical vapour deposition.