FeN_4掺杂对富勒烯催化特性调制的第一性原理研究

因其较好的稳定性和催化活性,非金属N与金属共掺杂的富勒烯(C60)作为新型氧化还原反应(ORR)催化剂受到了人们的广泛关注.采用基于密度泛函理论的第一性原理方法系统地研究了Fe N4掺杂对C60催化特性的调制规律,揭示了O_2在Fe N4掺杂的C60上的吸附和氢化特性.结果表明:(1)O_2倾向于以side-on模式吸附在Fe的顶位上,O-O键平行于C60的球切面,与Fe形成O-Fe-O三元环结构,对应的吸附能为1.48 e V.(2)O_2的氢化反应路径可以分为两条:(i)O_2先解离为O+O,然后氢化为O+OH.O_2的解离为反应的速控步,势垒为2.82 e V.(ii)O_2先氢化形成OOH结构,然后解离.氢化为反应的速控步,势垒为2.83 e V.     

O_2在FeN_4掺杂碳纳米管上氢化特性的密度泛函理论研究

因其速率快、稳定性高,非金属N与金属共掺杂的碳材料作为新型高效ORR催化剂而引起了人们的广泛关注.采用包含色散力校正的密度泛函理论方法系统地研究了氧分子在FeN_4掺杂的碳纳米管上的吸附、氢化特性.结果表明:(1)O_2倾向于以end-on模式吸附在Fe顶位,O-O键与衬底表面成一定角度,并指向五元环,对应的吸附能为1.62 e V.(2)O_2在FeN_4-CNTs上更倾向于直接氢化为OOH,然后解离为O+OH,整个路径的限速步为OOH的解离,对应的势垒为1.19 eV.     

第一性原理研究O2在CrN4掺杂石墨烯上的氢化

掺杂是调制graphene催化特性的有效方法. 掺杂的Graphene, 因其具有对氧还原反应具有较高的活性, 而作为一种新型高效质子交换膜燃料电池阴极材料. 采用包含色散力校正的第一性原理的密度泛函理论方法(DFT-D)系统的研究了O2在CrN4掺杂的Graphene上的吸附和氢化特性. 结果表明: (1) O2倾向于以side-on模式吸附在Cr顶位, 形成O-Cr-O三元环结构, 吸附能为1.75 eV; (2) O2在CrN4-Gra上更倾向于直接分解成O+O, 并进一步氢化为O+OH, 反应的限速步为O2的分解, 相应的反应势垒为0.48 eV.     

第一性原理研究O2在TiN4掺杂石墨烯上的氢化

作为一种新型高效质子交换膜燃料电池阴极材料, 金属与N共掺杂的石墨烯因其对氧还原反应具有较高的活性而引起了人们的广泛关注. 采用包含色散力校正的密度泛函理论方法系统地研究了O₂在TiN₄掺杂的Graphene上的吸附, 氢化特性. 结果表明: 1) O₂倾向于以side-on模式吸附在Ti顶位, 形成O-Ti-O三元环结构; 2) O₂在TiN₄-Graphene上更倾向于以分子形式直接氢化, 形式OOH结构, 并进一步解离为O+OH, 反应的限速步为O₂的氢化, 对应的反应势垒为0.52 eV.     

第一性原理研究O_2在CrN_4掺杂石墨烯上的氢化

掺杂是调制graphene催化特性的有效方法 .掺杂的石墨烯,因其具有对氧还原反应具有较高的活性,而作为一种新型高效质子交换膜燃料电池阴极材料.采用包含色散力校正的第一性原理的密度泛函理论方法 (DFT-D)系统的研究了O_2在CrN_4掺杂的石墨烯上的吸附和氢化特性.结果表明:(1)O_2倾向于以side-on模式吸附在Cr顶位,形成O-Cr-O三元环结构,吸附能为1.75 e V;(2)O_2在Cr N4-Gra上更倾向于直接分解成O+O,并进一步氢化为O+OH,反应的限速步为O_2的分解,相应的反应势垒为0.48 e V.     

O2在Si掺杂石墨烯上吸附与活化

采用包含色散力校正的密度泛函理论方法(DFT-D)研究了O2在Si掺杂石墨烯(Si-Gra)上吸附与活化. 研究结果表明: 1) 与纯净石墨烯相比, Si掺杂极大的增强了石墨烯对O2的吸附能力. O2的最稳定吸附构型是以Side-on 模式吸附在掺杂的Si的顶位, 形成O-Si-O三元环. 次稳定吸附构型是与Si及近邻的一个C形成O-Si-C-O四元环结构. 两个吸附构型对应的吸附能分别为-2.40和-1.93 eV; 2) O2有两种分解路径: 直接分解路径(势垒为0.53 eV)和整体扩散后的分解路径(势垒为0.81 eV); 3) 分解之后的两个O原子分别吸附在Si的顶位和相邻碳环的两个碳原子的桥位; 4) 电子结构分析表明吸附的O2从Si-Gra获得较多电荷, 从而被活化. 总之, Si-Gra具有较强的催化氧气还原能力, 是一种潜在的良好的非金属氧还原催化剂.     

O_2在Si掺杂石墨烯上吸附与活化

采用包含色散力校正的密度泛函理论方法(DFT-D)研究了O2在Si掺杂石墨烯(Si-Gra)上吸附与活化.研究结果表明:1)与纯净石墨烯相比,Si掺杂极大的增强了石墨烯对O2的吸附能力.O2的最稳定吸附构型是以Side-on模式吸附在掺杂的Si的顶位,形成O-Si-O三元环.次稳定吸附构型是与Si及近邻的一个C形成O-Si-C-O四元环结构.两个吸附构型对应的吸附能分别为-2.40和-1.93eV;2)O2有两种分解路径:直接分解路径(势垒为0.53eV)和整体扩散后的分解路径(势垒为0.81eV);3)分解之后的两个O原子分别吸附在Si的顶位和相邻碳环的两个碳原子的桥位;4)电子结构分析表明吸附的O2从Si-Gra获得较多电荷,从而被活化.总之,Si-Gra具有较强的催化氧气还原能力,是一种潜在的良好的非金属氧还原催化剂.     

Li修饰的C_6分子对H_2O的吸附研究

采用密度泛函理论中的广义梯度近似研究C6Li吸附H2O分子并将之进行分解的催化过程.几何优化发现:Li原子最稳定的吸附位置是位于C原子顶位上方.研究表明,第一个H2O分子吸附在C6Li上需要克服1.77 eV的能量势垒,然后分解为H和OH且与Li原子成键.当吸附第二个H2O分子时,第二个H2O分子需要克服1.2 eV的能量势垒分解为H和OH,其中H与Li原子上的H原子结合成H2,OH则替代Li原子上的H结合在Li原子上.因此C6Li可以作为催化剂将H2O分子进行分解得到H2.分析可知:C6Li主要是通过Li原子与H2O之间形成的偶极矩作用来吸附H2O分子,与C60Li12的储氢机制类似.研究结果可为储氢材料的制备提供一个新的思路.     

B,P单掺杂和共掺杂石墨烯对O,O_2,OH和OOH吸附特性的密度泛函研究

基于第一性原理的密度泛函理论研究了B,P单掺杂以及B,P共掺杂石墨烯对O,O_2,OH和OOH的吸附特性.通过分析吸附能、键长、态密度以及电荷转移,比较了不同掺杂对燃料电池氧还原反应(ORR)中间物吸附的影响,进而探讨了反应过程,并给出各步反应自由能的变化趋势.结果表明:B,P单掺杂石墨烯对各中间物的吸附能存在线性关系,掺P石墨烯吸附OOH的吸附能为3.26 eV,远大于掺B石墨烯的吸附能0.73 eV;掺P石墨烯较大的吸附能有利于中间物OOH中O—O键的断裂,掺B石墨烯吸附能小有利于中间物OH生成H2O脱附的反应发生;而B,P共掺杂石墨烯的吸附存在协同效应,具有更好的催化ORR的反应能力.     

Pu(100)表面吸附CO2的密度泛函研究

采用广义梯度密度泛函理论的改进Perdew-Burke-Ernzerh方法结合周期性层晶模型,研究了CO₂分子在Pu（100）面上的吸附和解离.吸附能和几何构型的计算表明,CO₂以穴位C4O4构型吸附最为有利,吸附能为1.48 eV.布居分析和态密度分析表明,CO₂与Pu表面相互作用的本质主要是CO₂分子的杂化轨道2π_μ与Pu5f,Pu6d,Pu7s轨道通过强电子转移和弱重叠杂化的方式相互作用而生成了新的化学键.计算的CO₂→CO+O解离能垒为0.66 eV,解离吸附能为2.65 eV, 表明在一定热激活条件下CO₂分子倾向于发生解离性吸附.O₂,H₂,CO和CO₂在Pu （100）面吸附的比较分析表明,较低温度下的吸附强度顺序依次为O₂,CO,CO₂,H₂;较高温度下的吸附强度顺序依次为O₂,CO₂,CO,H₂. 关键词： 密度泛函理论 Pu （100） 2')" href="#">CO₂ 吸附和解离     

Adsorption and decomposition of H2O on a K-covered Pt(111) surface

The adsorption of H₂O on clean and K-covered Pt(111) was investigated by utilizing Auger, X-ray and ultra-violet photoemission spectroscopies. The adsorption on Pt(111) at 100–150 K was purely molecular (ice formation) in agreement with previous work. No dissociation of this adsorbed H₂O was noted on heating to higher temperatures. On the other hand, adsorption of H₂O on Pt(111) + K leads to dissociation and to the formation of OH species which were characterized by a work function increase, an O 1s binding energy of 530.9 eV and UPS peaks at 4.7 and 8.7 eV below the Fermi level. The amount of OH formed was proportional to the K coverage for θ_K > 0.06 whereas no OH could be detected for θ? 0.06. Dissociation of H₂O occurred already at T = 100 K, with a sequential appearance of O 1s peaks at 531 and 533 eV representing OH and adsorbed H₂O, respectively. At room temperature and above only the OH species was observed. Annealing of the surface covered with coadsorbed K/OH indicated the high stability of this OH species which could be detected spectroscopically up to 570 K. The adsorption energy of H₂O coadsorbed with K and OH on Pt(111) is increased relative to that of H₂O on Pt. The work function due to this adsorbed H₂O increases whereas it decreases for H₂O on Pt(111). The energy shifts of valence and O1s core levels of H₂O on Pt + K as deduced from a comparison of gas phase and adsorbate spectra are 2.8–4.2 eV compared to ≈ 1.3–2.3 eV for H₂O on Pt (111). This increased relaxation energy shift suggests a charge transfer screening process for H₂O on Pt + K possibly involving the unoccupied 4a₁ orbital of H₂O. The occurrence of this mode of screening would be consistent with the higher adsorption energy of H₂O on Pt + K and with its high propensity to dissociate into OH and H.     

Structural effects on water formation from coadsorbed H + O on Rh(100)

The effect of adsorbate coverage, adsorption sequence and temperature on the structure, composition and reactivity of coadsorbed layers, produced by dissociative adsorption of O₂ and H₂ at 200 K on a Rh(100) surface, has been studied by combined TPD, XPS and LEED measurements. The emphasis is on the impact of the structure and composition of the mixed O + H layers on the synthesis of hydroxyl and water as a result of the O + H surface reaction. The difference in the O 1s binding energies of adsorbed O (529.9 eV) and OH species (530.8 eV) was used as a fingerprint to monitor the formation of the OH species. The H₂O TPD spectra show substantial variations of the desorption temperature range and the amount of water evolved with coadsorbate coverage and structure: from 270 to 350 K and from 0 to 0.08 ML, respectively. It has been found that dense O + H adlayers, where the O coverage is in the range 0.25-0.4 ML, favor the formation of stable OH species. The maximum amount of stable hydroxyl OH species ( 0.16 ML) can be produced by heating of these dense adlayers to 260 K. This results in reordering of the adspecies to form a new O + OH − (2 × 6) structure, where hydroxyls react readily to evolve 0.08 ML of water in a sharp desorption peak at 280 K. The effect of the adlayer density and restructuring on the production of OH and H₂O is discussed.     

Mechanistic understanding of hydrogenation of acetaldehyde on Au(111): A DFT investigation

This paper describes the reaction pathways for hydrogenation of acetaldehyde on atomic hydrogen pre-adsorbed Au(111) employing density functional theory (DFT) calculations. All the surface species involved in the reaction scheme have low diffusion barriers, suggesting that the rearrangement and movement of these species on the surface are facile under reaction condition. The hydroxyethyl is proposed to be the intermediate for the hydrogenation of acetaldehyde, and the activation energy for its formation is 0.37 eV. Additionally, the coupling reaction of hydroxyethyl and acetaldehyde – resulting in the formation of the ethylidene ethylene glycol (CH₃C^?HOCH(CH₃)OH) species – also readily occurs at the reaction condition. Two-dimensional (2-D) polyacetaldehyde ((CH₃CHO)₂) can be easily hydrogenated to ethylidene ethylene glycol or ethoxy hemiacetal (CH₃CH₂OCH(CH₃)O^?); the latter can be converted to ethanol and acetaldehyde via further hydrogenation. As the hydrogenation products of ethylidene ethylene glycol and ethoxy hemiacetal, ethoxyethanol (CH₃CH₂OCH(CH₃)OH) can be deeply hydrogenated to hydroxyethyl and ethanol. Our calculations also suggest that the formation of an ethoxyl intermediate is not likely, which agrees with the experimental observation that no deuterated acetaldehydes have been detected in isotopic measurements.