基于后功能化工艺修饰类石墨相氮化碳及其光催化产氢性能研究（英文）

本研究设计了一种后功能化工艺方法修饰类石墨相氮化炭材料。通过此工艺成功得到了硼掺杂的介孔氮化炭材料,该材料比表面积高达125 m²/g,这为提升光催化分解水性能奠定了基础。利用X射线衍射、X射线光电子能谱,荧光光谱和紫外-可见光谱对材料进行了全面的表征。基于X射线光电子能谱分析,发现通过后功能化处理硼原子成功掺杂进入氮化炭的晶格中;通过吸收光谱分析得知,硼掺杂的介孔氮化炭材料增强了在可见光区的光吸收;通过荧光光谱分析得知,相比原始氮化炭材料,硼掺杂后的介孔氮化炭材料有着更低的荧光强度,意味着光生电子和空穴的分离得到了提升。对材料进行光催化分解水测试,后功能化处理得到的硼掺杂介孔氮化炭材料的产氢速率是原始氮化炭材料的10.2倍。此结论对后续利用后功能化工艺修饰材料提升材料性能具有一定的借鉴意义。     

有序介孔石墨相氮化碳的合成及催化Knoevenagel缩合研究

以二氰二胺为前驱体,不同晶化温度的SBA-15为硬模板,用纳米浇铸法合成了一系列比表面和孔体积可调的介孔石墨相氮化碳(CND-SBA15)。通过N2吸-脱附、TEM、小角XRD、XPS、FT IR、CO2-TPD等手段研究了材料的织构、微观形貌、孔结构的有序性、化学组成和碱性质等。在以苯甲醛和丙二腈为底物的Knoevenagel缩合反应中,CND-SBA15材料表现出了很好的催化活性和稳定性。     

介孔类石墨氮化碳的制备及其催化Knoevenagel缩合反应

以氰胺为前驱体,通过胶态纳米氧化硅小球模板法,制备了一系列介孔类石墨氮化碳材料(mpg-C3N4)。通过X射线衍射、N2吸附-脱附、透射电镜、红外光谱、元素分析等手段对mpg-C3N4的结构和形貌等理化性质进行了表征。结果发现,通过调控硬模板和前驱体的用量可以获得比表面(190～301m2/g)和孔体积(0.65～1.07cm3/g)可调的mpg-C3N4材料。以Knoevenagel缩合为探针反应研究了mpg-C3N4的催化性能,结果显示,在以苯甲醛和丙二腈为底物的缩合反应中,去质子化mpg-C3N4表现出良好的催化性能。经简单分离后催化剂可重复使用5次以上且活性基本保持不变。     

介孔分子筛MCM-48的氮化与表面胺化及其碱催化反应性能

以介孔分子筛MCM-48为前驱体,通过表面胺化和高温NH3氮化方法制备出两种碱性分子筛.采用X射线衍射(XRD)、N2-吸附脱附、透射电镜(TEM)、红外光谱(FT-IR)、热重分析(TG)和哈密特指示剂法对上述分子筛的结构及表面酸碱性进行了详细表征,并通过苯甲醛与丙二腈的Knoevenagel缩合反应对其碱催化活性及稳定性进行了考察和对比.结果表明,表面胺化和高温氮化的方法均可制备出碱性介孔分子筛,且均在Knoevenagel碱性探针反应中表现出较好的碱催化活性,但与后者相比,前者制备的碱性分子筛具有更强的表面碱性和更好的反应稳定性.     

超薄骨架有序介孔CdS/NiS的制备及光催化产氢性能

采用有序介孔氧化硅为硬模板, 通过纳米浇筑法制备了由螺旋骨架构建的有序介孔硫化镉(CdS)光 催化材料. 该光催化材料具有约5 nm厚的超薄骨架和大的比表面积(238 m²/g), 能有效缩短光催化反应中 光生电荷迁移到表面进行反应的距离并同时提供更多的反应活性位点, 从而增强光催化性能. 通过原位化学沉积法将不同量的助催化剂硫化镍(NiS)沉积到有序介孔CdS表面, 得到了一系列超薄骨架有序介孔CdS/NiS复合光催化材料. 可见光照射下的光催化产氢活性测试结果表明, 负载适量NiS的有序介孔CdS具有显著增强的光催化产氢活性(3.84 mmol?h^-1?g^-1), 约为负载相同量NiS的普通商业化CdS材料(0.22 mmol?h^-1?g^-1)的17.5倍.     

高比表面积等级孔γ-Al2O3的金属醇酯一步水解法制备及性能

采用金属醇酯一步水解法, 在不同含水有机溶剂反应介质中在常温条件下制备了具有特殊形貌及等级孔道结构的超高比表面积γ-Al₂O₃材料. X射线衍射(XRD)、 N₂吸附-脱附、 扫描电子显微镜(SEM)和透射电子显微镜(TEM)等表征结果证明, 通过调节反应介质中水含量和溶剂类型可以精确控制仲丁醇铝的水解缩合反应过程和副产物醇分子的扩散行为, 进而优化产物的孔道结构. 研究结果表明, 在水/乙腈体系下制备的γ-Al₂O₃材料整体呈现出由大孔直孔道和三维介孔孔道构成的等级孔道结构, 且随着水含量的增加, 大孔孔壁依次出现光滑状、 片状和褶皱状的特定形貌; 在饱和水的丁醇溶液体系下制备的材料则展现出由厚度约为10 nm的片状γ-Al₂O₃堆积而成的三维介孔结构, 比表面积高达517 m ²/g. 选取水含量为3 mL的水/乙腈体系下的大孔-介孔γ-Al₂O₃材料作为载体制备负载型Pt基催化剂. 负载后载体等级孔结构基本保持完好, 金属Pt纳米颗粒均匀分散在载体上, 该催化剂在渣油脱金属催化反应中的脱金属性能比商用薄水铝石为载体制备Pt基催化剂更加优异. 脱Ni率和脱V率分别提高11.62%和10.83%.     

介孔碳的快速水相合成及对辣根过氧化物酶的固定

以间苯三酚-甲醛为碳源前驱体, 嵌段聚合物F127 (PEO₁₀₆PPO₇₀PEO₁₀₆)为模板剂, 在水相中快速合成了介孔碳材料. 将其应用于辣根过氧化物酶的固定化, 并初步研究了固定化对酶稳定性的影响. 利用TEM和SEM观察该材料的微观结构, 通过N₂吸附-脱附技术对介孔碳材料的孔结构和孔容等进行了表征. 结果表明, 介孔碳材料具有蠕虫状介孔结构, 孔径可在5.6～7.6 nm之间调变, 相应的比表面积介于691.1～787.8 m²/g, 且随着反应体系中盐酸浓度的增加, 所得材料的孔径、比表面积和孔容等均呈现减小的趋势. 固定在介孔碳中的辣根过氧化物酶, 保持了其蛋白质二级结构, 且与游离酶相比, 固定化酶的热稳定性、pH稳定性和操作稳定性都有明显的提高. 经多次循环操作, 固定化酶依然保持较高的活性, 说明其具有良好的可重复利用价值.     

MCM-41 负载席夫碱催化α,β-不饱和酮的环氧化反应研究

介孔分子筛MCM-41 依次与3-氯丙基三乙氧基硅烷、环己二胺和三唑醛反应, 得到席夫碱修饰的新型介孔分子筛MCM-41 催化剂. 通过傅里叶变换红外光谱(FTIR)和X 射线多晶衍射(XRD)等方法对所得催化剂进行表征. 以过氧化氢为氧源, 介孔分子筛MCM-41 负载的席夫碱为催化剂, 研究了α,β-不饱和酮的环氧化反应, 考察了金属盐、溶剂、催化剂用量、反应时间等因素对环氧化反应的影响. 结果表明, 在室温下乙腈溶剂中, α,β-不饱和酮的环氧化反应在短时间内均以很高的产率(高达99%)得到了相应的产物. 同时, 对催化剂的重复利用进行了研究, 发现重复使用四次, 仍能以较高产率得到环氧化产物.     

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。     

等级孔微孔-介孔Fe2O3/ZSM-5中空分子筛催化材料的制备及催化苄基化性能

ZSM-5分子筛具有极其均匀的孔道结构、 良好的形状选择性和催化活性及耐水热稳定性, 是一种高效、 绿色的固体催化剂, 被广泛应用于石油催化裂化、 精细化工和环境保护等领域. 但其单一的微孔结构大大降低了客体分子的流通扩散性, 导致由大分子参与的芳烃烷基化反应受到极大限制. 本文采用NaOH/四丙基氢氧化铵(TPAOH)混合碱处理微孔ZSM-5, 制备了具备高结晶度、 高比表面积的等级孔微孔-介孔ZSM-5中空分子筛材料, 该材料在保持微孔孔道良好水热稳定性和大量活性中心的同时, 还通过介孔的引入进一步促进反应物及产物的扩散, 使间三甲苯苄基化反应的转化率提高了3.8倍. 通过在等级孔微孔-介孔ZSM-5中空材料上负载Fe, 开发出了具有双功能的等级孔微孔-介孔Fe₂O₃/ZSM-5中空催化剂, 该催化剂在苯的苄基化反应中表现出优异的催化性能, 当Fe负载量(质量分数)为6.67%, 反应温度为75 ℃, 反应时间为15 min时, 转化率高达98.3%, 选择性为81.6%, 最终收率达到80.2%.     

Time‐of‐flight secondary ion mass spectroscopic characterization of the nitrogen profile of shallow gate oxynitride thermally grown on a silicon substrate

Silicon oxynitride has been used as a shallow gate oxide material for microelectronics and its thickness has been reduced over the years to only a few tens of angstroms due to device size scaling. The nitride distribution and density characteristic in the gate oxide thus becomes imperative for the devices. The shallow depth profiling capability using time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) has huge potential for the nitrogen characterization of the shallow gate oxide film. In this article, both positive and negative spectra of TOF‐SIMS on silicon oxynitride have been extensively studied and it was found that the silicon nitride clusters Si_xN^? (x = 1–4) are able to represent the nitrogen profiles because their ion yields are high enough, especially for the low‐level nitride doping in the oxide, which is formed by the annealing of nitric oxide on SiO₂/Si. The gate oxide thickness measured by the TOF‐SIMS profiling method using ¹⁸O or CsO profile calibration was found to correlate very well with transmission electron microscope measurement. The nitrogen concentration in the gate oxide measured using the TOF‐SIMS method was consistent with the results obtained using the dynamic SIMS method, which is currently applied to relatively thicker oxynitride films. Copyright © 2012 John Wiley & Sons, Ltd.     

Separation behavior of basic compounds on unbonded silicon oxynitride and silica high‐performance liquid chromatography stationary phases with reversed‐phase eluents

Unbonded silicon oxynitride and silica high‐performance liquid chromatography stationary phases have been evaluated and compared for the separation of basic compounds of differing molecular weight, pK_a, and log D using aqueous/organic mobile phases. The influences of percentage of organic modifier, buffer pH, and concentration in the mobile phase on base retention were investigated on unbonded silicon oxynitride and silica phases. The results confirmed that unbonded silicon oxynitride and silica phases demonstrated excellent separation performance for model basic compounds and both the unbonded phases examined possessed a hydrophobic/adsorption and ion‐exchange character. The silicon oxynitride stationary phase exhibited high hydrophilicity compared with silica with a reversed‐phase mobile phase. An ion‐exclusion‐type mechanism becomes predominant for the separation of three aimed bases on the silicon oxynitride column at pH 2.8. Different from silicon oxynitride stationary phase, no obvious change for the retention time of three model bases on silica stationary phase at pH 2.8 can be observed.     

One-Step Synthesis of Silicon Oxynitride Films Using a Steady-State and High-Flux Helicon-Wave Excited Nitrogen Plasma

A steady-state and high-flux helicon-wave excited N₂ plasma was used to oxynitride Si substrates for the synthesis of silicon oxynitride (SiON) films. X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) have been extensively used to characterize surface quality of the SiON films, and it is found that a large amount of nitrogen (N) can be incorporated into the films. The result of XPS depth profiles shows that the N concentration is high near the surface and the oxide/Si interface. In the UPS spectra, absence of the reappearance of surface states suggests a resistance to clustering of the oxynitride layer. The N₂ flux and Ar mixture quantity can facilitate tuning of the dissociation characteristics in N₂ discharge. By modulating the N₂ fractions, the N⁺ density reaches maximum at a N₂/(N₂ + Ar) flow-rate ratio of 0.5, resulting in incorporation of more N atoms into the SiON films. Considering the easy control of N₂ plasma, our work opens up a new avenue for achieving high-yield SiON films at low temperature.     

Niobium nitride films formed by rapid thermal processing (RTP): a study of depth profiles and interface reactions by complementary analytical techniques

The nitridation of niobium films approximately 250 and 650 nm thick by rapid thermal processing (RTP) at 800 °C in molecular nitrogen or ammonia was investigated. The niobium films were deposited by electron beam evaporation on silicon substrates covered by a 100 or 300 nm thick thermally grown SiO₂ layer. In these investigations the reactivity of ammonia and molecular nitrogen was compared with regard to nitride formation and reaction with the SiO₂ substrate layer. The phases formed were characterized by X-ray diffraction (XRD). Depth profiles of the elements in the films were recorded by use of secondary neutral mass spectrometry (SNMS). Microstructure and spatial distribution of the elements were imaged by transmission electron microscopy (TEM) and energy-filtered TEM (EFTEM). Electron energy loss spectra (EELS) were taken at selected positions to discriminate between different nitride, oxynitride, and oxide phases. The results provide clear evidence of the expected higher reactivity of ammonia in nitride formation and reaction with the SiO₂ substrate layer. Outdiffusion of oxygen into the niobium film and indiffusion of nitrogen from the surface of the film result in the formation of oxynitride in a zone adjacent to the Nb/SiO₂ interface. SNMS profiles of nitrogen reveal a distinct tail which is attributed to enhanced diffusion of nitrogen along grain boundaries.     

Quantitative analysis of silicon-oxynitride films by EPMA

Thin films of silicon oxynitride with diverse compositions were prepared by de-magnetron sputtering of silicon, utilising oxygen and nitrogen gas flows and the sputtering power to vary the composition. In order to investigate the composition of these films, a method of analysis by electron probe micro analysis with energy dispersive detection was developed and the figures of merit were compared to the wavelength dispersive method used by other authors. The precision and repeatability of the results are evaluated and the accuracy is checked by comparison with Rutherford backscattering and nuclear reaction analysis. Energy dispersive X-ray spectrometry was proven to be applicable to analyse silicon oxynitride films of any composition yielding quantitative results for nitrogen and oxygen as well as silicon. Besides the good analytical performance, electron probe micro analysis with energy dispersive X-ray spectrometry has turned out to be a non-destructive, quick, easy to use and cost effective tool for the routine analysis of light elements in thin films.     

Vanadium Nitride Films Formed by Rapid Thermal Processing (RTP): Depth Profiles and Interface Reactions Studied by Complementary Analytical Techniques

The nitridation of vanadium films in molecular nitrogen and ammonia using a RTP‐system was investigated. The V films were deposited on silicon substrates covered by 100 nm thermal SiO₂. For a few experiments sapphire substrates were used. Nitride formation at high temperatures (900 and 1100 °C) and interface reactions and diffusion of oxygen out of the SiO₂‐layer into the metal lattice at moderate temperatures (600 and 700 °C) were studied. For characterisation complementary analytical methods were used: X‐ray diffraction (XRD) for phase analysis, secondary neutral mass spectrometry (SNMS) and Rutherford Backscattering (RBS) for acquisition of depth profiles of V, N, O, C and Si, transmission electron microscopy (TEM) in combination with electron energy filtering for imaging element distributions (EFTEM) and recording electron energy loss spectra (EELS) to obtain detailed information about the initial stages of nitride, oxide and oxynitride formation, respectively, and the microstructure and element distributions of the films. In these experiments the SiO₂‐layer acts as diffusion barrier for nitrogen and source for oxygen causing the formation of substoichiometric vanadium oxides and oxynitrides near the V/SiO₂‐interface primarily at temperatures ≤ 900 °C. At a temperature of 1100 °C just a small amount of oxynitride forms near the interface because rapid diffusion of nitrogen and fast formation of VN (diffusion barrier for oxygen) inhibit the outdiffusion of oxygen into the metal layer. In the 600 °C regime, in argon atmosphere oxynitride phases observed in the surface region of these films originate from reaction of residual oxygen in the argon gas, whereas NH₃ as process gas does not lead to oxide or oxynitride formation at the surface (apart from the oxidation caused by storage). NH₃ seems to support the diffusion of oxygen out of the SiO₂‐layer. During the decomposition of ammonia at higher temperatures hydrogen is formed, which could attack the SiO₂. In contrast, sapphire substrates do not act as oxygen source in the 600 °C regime and change the nitridation behaviour of the vanadium films.     

Formation and thermal decomposition of silicon oxynitride compounds I

The existence of formerly unknown compounds of the type M ₃ ¹ SiNO₂, suggested in previous papers, has been confirmed in reactions of lithium and sodium oxides with silicon oxynitride, Si₂N₂O.     

氮氧化硅反相色谱固定相材料的制备及色谱分离性能评价

硅胶是目前高效液相色谱(HPLC)固定相中应用最为广泛的基质材料,其流动相的最佳使用范围为pH 2～8。在高pH(pH＞8)的流动相条件下,流动相中的氢氧根会进攻硅胶基质表面残余的硅醇基,导致硅胶基质固定相骨架溶解。在前期的研究中,我们将高温氨气处理多孔硅胶微球得到的氮氧化硅材料用作HPLC固定相,氮氧化硅在高pH流动相条件下表现出了较硅胶更高的稳定性。本文利用元素分析对氮氧化硅材料的氮化程度及含氮量进行系统的表征,并考察了氮氧化硅材料在不同pH条件下的静态稳定性。利用十八烷基二甲基氯硅烷试剂对氮氧化硅材料表面进行疏水性修饰,并以元素分析和核磁共振波谱对表面键合氮氧化硅材料进行了表征。考察了不同碳链的烷基苯、酸性化合物、碱性化合物在疏水改性的C₁₈氮氧化硅反相色谱固定相上的色谱分离性能。进一步分别以酸、碱和中性化合物为分析对象,比较了C₁₈-SiON1050(10)与C₁₈-SiO₂色谱保留的差异。     

Toward accurate characterization of nitrogen depth profiles in ultrathin oxynitride films

Good accuracy in depth profile analyses of nitrogen in ultrathin oxynitride films is desirable for process development and routine process monitoring. Low energy SIMS is one of the techniques that has found success in the accurate characterization of thin oxynitride films. This work investigated the artifacts in a typical depth profile analysis of nitrogen with the current SIMS technique and the ways to improve the accuracy by selecting optimal analytical conditions. It was demonstrated that surface roughness developed rapidly in a SiO₂/Si stack when it was bombarded with an O₂⁺ beam at 250 eV and angle of incidence from 70 to 79° . The roughness caused distortion in the measured depth profiles of nitrogen and the major component elements. However, the above roughness and the distortion in the depth profiles can be eliminated by using a 250 eV O₂⁺ beam at an angle of incidence above 80° . Depth profile analyses with a 250 eV 83° O₂⁺ beam exhibited minimal surface roughening and insignificant variation in the secondary ion yield of SiN^? from SiO₂ bulk to the SiO₂/Si interface, facilitating an accurate analysis of nitrogen distribution in a SiO₂/Si stack. In addition, depth profiles of the major component elements such as ¹⁸O^? and ²⁸Si^? delivered clear information on the location of the SiO₂/Si interface. Using the new approach, we compared nitrogen distribution in thin SiNO films with the decoupled‐plasma nitridation (DPN) at various powers. Copyright © 2008 John Wiley & Sons, Ltd.     

A nuclear microprobe method for the simultaneous determination of silicon and nitrogen profiles in metals

A nuclear microprobe method has been developed for the simultaneous determination of silicon and nitrogen concentration profiles in metals. The method was based on the reactions²⁸Si(d, p₀)²⁹Si and¹⁴N(d, p₀)¹⁵N plus¹⁴N(d, β₀)¹²C with measurement of emitted charged particles during irradiation with 1.9 MeV deuterons. The nitrogen sensitivity was ten times that for silicon and the minimum concentrations detected were 0.002% and 0.03% respectively. The method was successfully applied to the measurement of silicon and nitrogen profiles in alloys contacted with silicon nitride at high temperature.