Hydrogen adsorption and desorption on the Pt and Pd subnano clusters – a review

In this review, we present our recent first principles studies on the sequential H₂ dissociative chemisorption and H desorption on the Pt_n and Pd_n clusters (n=2-9, 13). Upon full saturation by H atoms, the calculated H₂ dissociative chemisorption energy and H desorption energy on Pt₁₃ and Pd₁₃ clusters are similar to the corresponding values on smaller close-packed clusters. Indeed, the catalytic performances of these subnano clusters do not vary significantly with the particle sizes or shapes. Instead, they are dependent on the surface metal atoms which can be accessed by H atoms. In addition to the coverage dependency of the H₂dissociative chemisorption and H sequential desorption energies, the phase transition of both Pt₁₃ and Pd₁₃from the icosahedral to fcc-like structures at certain H coverage was also investigated.     

碳硼富勒烯衍生物C18B2M(M=Li,Ti, Fe)的储氢性能计算研究

本文使用密度泛函理论(density functional theory, DFT)中的广义梯度近似(generalized gradient approximation, GGA)研究了经碱金属原子Li、过渡金属原子Ti和Fe原子修饰的富勒烯C₁₈B₂M(M=Li, Ti, Fe)的储氢性能. 研究发现, C₁₈B₂由于B的替代掺杂, 比C₂₀对金属原子具有更高的结合能. 由平均吸附能分析可知: C₁₈B₂Li对H₂的吸附能力较弱, C₁₈B₂Fe对H₂的吸附能力过强, 而C₁₈B₂Ti对H₂的平均吸附能介于0.45-0.59 eV 之间, 介于物理吸附和化学吸附之间 (0.2-0.6 eV), 因此可以实现常温下的可逆储氢. C₁₈B₂M(M=Li, Ti, Fe)能够吸附的H₂数目最多分别为4, 6和4. 由储氢机理分析可知: C₁₈B₂Li主要通过碱金属离子激发的静电场来吸附H₂, 而C₁₈B₂Ti和C₁₈B₂Fe主要通过金属原子与H₂之间的Kubas作用来吸附H₂. 由于C₁₈B₂Ti既有较大的储氢数目, 又可以实现可逆储氢, 因此有望开发成新型纳米储氢材料.     

Three-Ni-atom cluster formed by sulfur adsorption on Ni(1 1 1)

Sulfur adsorption on Ni(1 1 1) at room temperature has been studied by scanning tunneling microscopy. Irregularly-shaped islands, which are aggregates of small particles, appear with troughs on (1 1 1) terraces. Estimating the number of small particles in the irregular islands and that of Ni atoms ejected through the formation of troughs, we find that each small particle contains three Ni atoms. A three-Ni-atom cluster is proposed, where three S atoms are adsorbed on 4-fold hollow sites formed on the sides of the cluster. The Ni₃S₃ cluster can assume two orientations on the (1 1 1) surface. We show that the apparently-irregular distribution of small particles is well understood by assuming the alternate orientation of neighboring Ni₃S₃ clusters and the slight energy difference between the two orientations of a single Ni₃S₃ cluster. Real-time observation of a Ni(1 1 1) surface under H₂S ambience reveals that small islands composed of three or four Ni₃S₃ clusters change their positions rapidly, preventing the simple growth of islands at the initially-nucleated positions.     

石墨烯在Al_2O_3(0001)表面生长的模拟研究

基于密度泛函理论的广义梯度近似法,对用化学气相沉积法在蓝宝石(α-Al_2O_3)(0001)表面上生长石墨烯进行理论研究.研究结果表明:CH_4在α-Al_2O_3(0001)表面上的分解是吸热过程,由CH_4完全分解出C需要较高能量及反应能垒,这些因素不利于C在衬底表面的存在.在α-Al_2O_3(0001)表面,石墨烯形核的活跃因子并不是通常认为的C原子,而是CH基团.通过CH基团在α-Al_2O_3(0001)表面上的迁移聚集首先形成能量较低的(CH)_x结构.模拟研究(CH)_x对揭示后续石墨烯的形核生长机理具有重要意义.     

The structure of a metallic glass system using EXELFS and EXAFS as complementary probes

The short-range atomic order around all three constituent atoms in a prototypical bulk metallic glass (BMG) system was probed in a complementary way, using extended X-ray absorption fine structure for neighborhood of the higher atomic number elements, and extended energy loss fine structure (EXELFS) for the lower atomic number ones. The Pd_xNi_(80−x)P₍₂₀₎ system is a prototype for a whole class of BMG formers which are 80% transition metal and 20% metalloid. We find that the structure of these BMGs could be explained in terms of those of glasses at the end of the BMG range, namely, Pd₆₀Ni₂₀P₂₀ and Pd₃₀Ni₅₀P₂₀. The binary phosphide crystals near x=0 and 80 are found to be simulate very well the local atomic structure of Pd₃₀Ni₅₀P₂₀ and Pd₆₀Ni₂₀P₂₀ glasses, respectively. The best glass former in this series, Pd₄₀Ni₄₀P₂₀, is best described by a weighted average of Pd₃₀Ni₅₀P₂₀ and Pd₆₀Ni₂₀P₂₀ structures.     

Magneto-optical and magnetic properties of some solid solutions of C1b-Heusler compounds

The large Kerr effect in PtMnSb has been ascribed to details of its unusual band structure. Substitution of atoms will modify the band structure and consequently alter the Kerr effect. In the present investigation we have determined the magneto-optical properties at room temperature in the energy range 0.5–5 eV of several solid solutions of C1_b−Heusler compounds, comprising the solid solution series Pt_1−xNi_xMnSb, Pt_1−xRh_xMnSb, Ni_1−xCr_xMnSb, Ni_1−xFe_xMnSb and PtMnSb_0.9Sn_0.1. The magnetic and crystallographic properties were determined for the solid solution series Pt_1−xNi_xMnSb, Pt_1−xRh_xMnSb and Ni_1−xCr_xMnSb. Neither of the substitutions leads to a larger Kerr effect than that present in the pure compound. Moreover, it is found that the shape of the spectra does not change significantly. For one case, Ni substituted in PtMnSb, band structure calculations were made for hypothetically ordered compounds. The results agree with the experimental findings that near 1.7 eV magneto-optically active transitions persist on substituting Ni in PtMnSb.     

钚氧化物中氢行为的第一性原理研究

通过第一性原理计算和原子级热力学方法,系统研究H、H₂在PuO₂和α-Pu₂O₃中的吸附、扩散和溶解行为.研究发现：氢的上述行为均是吸热过程,但在α-Pu₂O₃与PuO₂中有显著不同：在α-Pu₂O₃中H可自发聚合成H₂,但在PuO₂中H难再聚合;在α-Pu₂O₃中H、H₂均能扩散,通常H会聚合成H₂再扩散,在PuO₂中H₂解离后才能扩散,且PuO₂中H沿高势能面的扩散比α-Pu₂O₃中H₂扩散更容易;在氢压、温度驱动下,氢在α-Pu₂O₃中存在H₂溶解到H+H₂混合溶解机制的转变,平衡气压P_H2远小于H在PuO₂中溶解的情况.基于此,给出PuO₂和α-Pu₂O₃中氢行为的微观图像和PuO₂的阻氢微观机制：PuO₂表面限制H₂解离、渗透,PuO₂块体限制H的溶解,但不阻止H扩散.结合钚氧化层表面氢行为研究获得了钚氢化孕育期的微观机制,为孕育期全过程理论建模提供依据.     

各Li吸附组分下硅烯氢存储性能的第一性原理研究

利用Li原子对硅烯进行表面修饰是提高硅烯氢存储能力的一种有效方法.为了充分挖掘Li修饰硅烯的氢存储性能,本文采用范德瓦耳斯作用修正的第一性原理计算方法,对不同Li吸附组分下硅烯的结构、稳定性和氢存储能力进行了研究.研究结果表明,硅烯体系能够在Li组分从0.11增加到0.50时保持稳定,其最大储氢量随Li组分的增加而增大,氢气平均吸附能则存在减小趋势;当Li组分达到0.50而饱和时,硅烯体系具有最大的储氢量,相应的质量储氢密度为11.46 wt%,平均吸附能为0.34 eV/H2,远高于美国能源部设定的储氢标准,表明提高Li组分甚至使其达到饱和在理论上能有效提高Li修饰硅烯的储氢性能.此外,通过对Mulliken电荷布居、差分电荷密度和态密度的分析,发现Li修饰硅烯的储氢机制与电荷转移诱导的静电相互作用和轨道杂化作用有关.研究结果可为Li修饰硅烯在未来氢存储领域的应用提供理论指导.     

Li修饰的C24团簇的储氢性能

利用密度泛函理论研究了Li原子修饰的C₂₄团簇的储氢性能. Li原子在C₂₄团簇表面的最佳结合位是五元环. Li原子与C₂₄团簇之间的作用强于Li原子之间的相互作用, 能阻止它们在团簇表面发生聚集. 当Li原子结合到C₂₄表面时, 它们向C原子转移电子后带正电荷. 当氢分子接近这些Li原子时, 在电场作用下发生极化, 通过静电相互作用吸附在Li原子周围. 在Li修饰的C₂₄复合物中, 每个Li原子能吸附两到三个氢分子, 平均吸附能处于0.08到0.13 eV/H₂范围内. C₂₄Li₆能吸附12个氢分子, 储氢密度达到6.8 wt%.     

过渡族金属掺杂Al(111)表面对氢分子催化分解的影响

为了探求过渡金属催化剂对催化合成储氢材料NaAlH₄效果的影响, 本文采用第一性原理方法研究了多种金属原子取代Al (111)表面铝原子形成的合金表面对氢的催化分解的影响. 计算结果表明, Sc, V, Fe, Ti原子掺杂的表面对氢分子分解具有催化作用. H₂在对应的掺杂表面催化分解所需要的活化能分别为0.54 eV, 0.29 eV, 0.51 eV, 0.12 eV. H原子在Sc, V, Ti掺杂表面扩散需要的活化能分别为0.51 eV, 0.66 eV, 0.57 eV. 同时, 过渡金属掺杂在Al表面时倾向于分散分布, 增加掺杂表面的掺杂原子个数, 掺杂表面的催化效果体现为单个掺杂过渡金属原子的催化效果. 本研究将为金属掺杂Al (111)表面催化加氢合成NaAlH₄提供理论参考.     

分子动力学模拟H原子与Si的表面相互作用

通过分子动力学模拟了入射能量对H原子与晶Si表面相互作用的影响. 通过模拟数据与实验数据的比较, 得到H原子吸附率随入射量的增加 呈先增加后趋于平衡的趋势. 沉积的H原子在Si表面形成一层氢化非晶硅薄膜, 刻蚀产物(H₂, SiH₂, SiH₃和SiH₄)对H原子吸附率趋于平衡有重要影响, 并且也决定了样品的表面粗糙度. 当入射能量为1 eV时, 样品表面粗糙度最小. 随着入射能量的增加, 氢化非晶硅薄膜中各成分(SiH, SiH₂, SiH₃)的量以及分布均有所变化. 关键词： 分子动力学 吸附率 表面粗糙度 氢化非晶硅薄膜     

Quantitative determination of anti-structured defects applied to alloys of a wide chemical range

Anti-structured defects bridge atom migration among heterogeneous sublattices facilitating diffusion but could also result in the collapse of ordered structure.Component distribution Ni_(75)Al_xV_(25-x) alloys are investigated using a microscopic phase field model to illuminate relations between anti-structured defects and composition,precipitate order,precipitate type,and phase stability.The Ni_(75)Al_xV_(25-x) alloys undergo single Ni_3V(stage Ⅰ),dual Ni_3Al and Ni_3V(stage Ⅱ with Ni_3V prior;and stage Ⅲ with Ni_3Al prior),and single Ni_3Al(stage Ⅳ) with enhanced aluminum level.For Ni_3V phase,anti-structured defects(V_(Ni1),Niy,except V_(Ni2)) and substitution defects(Al_(Ni1),Al_(Ni2),Al_v) exhibit a positive correlation to aluminum in stage I,the positive trend becomes to negative correlation or smooth during stage Ⅱ.For Ni_3 Al phase,anti-structured defects(Al_(Ni),Ni_(Al)) and substitution defects(V_(Ni),V_(Al)) have a positive correlation to aluminum in stage Ⅱ,but Ni_(Al) goes down since stage Ⅲ and lasts to stage Ⅳ.V_(Ni) and V_(Al) fluctuate when Ni_3Al precipitates prior,but go down drastically in stageⅣ.Precipitate type conversion of single Ni_3V/dual(Ni_3V+Ni_3Al) affects Ni_3V defects,while dual(Ni_3V+Ni_3Al)/single Ni_3 Al has little effect on Ni_3Al defects.Precipitate order swap occurred in the dual phase region affects on Ni_3Al defects but not on Ni_3V.     

Li修饰的C$lt;sub$gt;6$lt;/sub$gt;分子对H$lt;sub$gt;2$lt;/sub$gt;O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. 关键词： 6')" href="#">C₆ Li 2O')" href="#">H₂O 密度泛函理论     

电场诱导(MgO)12储氢的从头计算研究

管状(MgO)₁₂是(MgO)_n的幻数团簇, 非常稳定. 为研究电场对其储氢性能的影响, 本文在B3LYP/6-31G^**水平上研究了电场中H₂在(MgO)₁₂管状结构上的吸附性质. 结果表明 (MgO)₁₂能承受强电场而保持管状结构并被极化, 其偶极矩增大为场强0.01 a.u. 和0.02 a.u.时的9.21和19.39 deb (1 deb=3.33564×10^-30C·m). H₂能稳定吸附在单个Mg/O原子上. 无电场时H₂在Mg上为侧位吸附, 而在O上为端位吸附; 电场中, H₂在Mg和O上均为端位吸附, 且其分子取向沿外电场方向. 由于(MgO)₁₂ 及H₂均被电场极化, 因此H₂在(MgO)₁₂部分位置上的吸附强度显著提高. H₂在3配位的Mg/O上的吸附能由无电场时0.08/0.06 eV分别提高到场强为0.01 a.u.和0.02 a.u.时的0.12/0.11 eV 和0.20/0.26 eV. 电子结构分析表明H₂吸附在Mg原子上时, 向团簇转移电荷, 电场极化效应是其吸附能较无电场时增大的主要原因. 吸附在O原子上时, 一方面由于O阴离子极化效应更强; 另一方面, H₂从(MgO)₁₂得到电荷, 其价轨道与团簇价轨道重叠形成化学键, 因此电场效应更显著. 电场中(MgO)₁₂最多能吸附16个H₂, 相应的质量密度为6.25 wt%.     

Spectroscopic Characterizations of Metal-Complexes of 4-Hydroxybenzoic Acid With the Ni(Ⅱ), Mn(Ⅱ), and Cu(Ⅱ) Ions

One of the phenolic acids is 4-hydroxybenzoic acid (HBA) which takes the form of a white crystalline solid with a molecular formula of C₇H₆O₃, a melting point of 214.5 ℃ and a molecular weight of 138.12 g·mol-1. It soluble in polar organic solvents like acetone and alcohols, and slightly soluble in chloroform and water. The reactions between the metal ions and the HBA were carried out under specific conditions like (molar reaction was 2∶2 (ligand to metal), reaction temperature was 60 ℃, media was neutral (pH 7), and solvent was H₂O ∶MeOH (1∶1). Under these conditions, the HBA was deprotonated to form (HOC₆H₄CO-₂; L-). The ligand L- was coordinated to the metal ions forming the metal complexation. The reaction of 4-hydroxybenzoic acid (HOC₆H₄CO₂H; HL) with the Ni(Ⅱ), Mn(Ⅱ) and Cu(Ⅱ) ions afford metal-complexes with gross formula of [Ni₂L₂(NO₃)₂(H₂O)₄], [Mn₂L₂(NO₃)₂(H₂O)₄] and [Cu₂L₂(NO₃)₂(H₂O)₄], respectively. These complexes were characterized by elemental analysis (CHN), magnetic susceptibility, UV-Vis spectra, infrared (IR), and X-ray powder diffraction (XRD) techniques. The complexes of HBA are insoluble in common solvents and hence molar conductance could not be measured, but this very insolubility indicates that the complexes are neutral. Data has demonstrated that the ligand (L-) was coordinated to the metal ion by bidentate bridging carboxylate group (COO-), with an octahedral geometry. Thus, HBA is expected to act as bidentate uninegative ions and the coordination number of the metal ions is six. XRD results showed that the complexes possess uniform and organized microstructures in the nanometer range with a main diameter in the range of 11～28 nm.     

Ni与钇稳定的氧化锆(111)表面相互作用以及界面活性的第一性原理研究

采用基于密度泛函理论的第一性原理方法, 系统研究了Ni原子在钇稳定的氧化锆(YSZ)(111)和富氧的YSZ(YSZ+O)(111)表面不同位置的吸附, 以及CO和O₂分子在Ni₁(单个镍原子)/YSZ和Ni₁/YSZ+O表面吸附的几何与电子结构特征. 结果表明: 1) 单个Ni原子倾向于吸附在O原子周围, 几乎不吸附在Y原子周围, 且Ni原子在氧空位上吸附最稳定; 2)和YSZ相比, 单个Ni原子在YSZ+O表面易发生氧化现象, Ni原子失去1.06 e电子, 被氧化成了Ni⁺, 吸附能力更强; 3)被氧化的Ni催化活性大幅下降, 大大减弱了表面对O₂和CO等燃料气体的吸附作用.     

Adsorption of hydrogen and deuterium on potassium-promoted Pd(100) surfaces

The adsorption of H₂ and D₂ has been studied on clean and K-promoted Pd(100) surfaces using thermal desorption, work function changes, ultraviolet photoelectron and Auger spectroscopy. The potassium adlayer significantly lowers the sticking coefficient (from 0.6 to 0.06 at θ_k = 0.2), and the uptake of hydrogen, but increases the desorption energy for H₂ desorption. Calculation showed that each potassium adatom blocks approximately 4–5 adsorption sites for H₂ adsorption. Atomization of hydrogen led to an increase of hydrogen uptake. The adsorption of potassium on the H-covered surface caused a significant decrease in the amount of hydrogen adsorbed on the surface (as indicated by less desorbing hydrogen below 500 K) and promoted the dissolution of H atoms into the bulk of Pd. The dissolved hydrogen was released only above 600–650 K. In the interpetation of the results the extended charge transfer from K-dosed Pd to the adsorbed H atoms and the direct interaction between adsorbed H and K adatoms are taken into account.     

Adsorption of potassium on a Si(111) surface

The adsorption of potassium on several sites (T₁, T₄, H₃) of a Si(111) surface is studied using the extended Hückel method and cluster models. The results show that the chemisorption energy on the T₄ site is almost equal to that on the H₃ site for an ideal surface. However, the analysis of chemical bonding of adatoms on a Si surface suggests that the chemisorption of adatoms might induce a kind of reconstruction on the Si(111) surface. Rough calculations for the adsorption on this reconstructed surface are carried out. In this paper, charge transfer, density of states and characterization of the bonds between the adatom and substrate Si atoms are also investigated in detail.     

C_9N_4 as excellent dual electrocatalyst: A first principles study

We perform first principles calculations to investigate the catalytic behavior of C_9 N_4 nanosheet for water splitting.For the pristine C_9 N_4,we find that,at different hydrogen coverages,two H atoms adsorbed on the 12-membered ring and one H atom adsorbed on the 9-membered ring show excellent performance of hydrogen evolution reaction(HER).Tensile strain could improve the catalytic ability of C_9 N_4 and strain can be practically introduced by building C_9 N_4/BiN,and C_9 N_4/GaAs heterojunctions.We demonstrate that the HER performance of heterojunctions is indeed improved compared with that of C_9 N_4 nanosheet.Anchoring transition metal atoms on C_9 N_4 is another strategy to apply strain.It shows that Rh@C_9 N_4 exhibits superior HER property with very low Gibbs free energy change of-30 meV.Under tensile strain within ～2%,Rh@C_9 N_4 could catalyze HER readily.Moreover,the catalyst Rh_9 C_9 N_4 works well for oxygen evolution reaction(OER)with an overpotential of 0.58 V.Our results suggest that Rh@C_9 N_4 is favorable for both HER and OER because of its metallic conductivity,close-zero Gibbs free energy change,and low oneset overpotential.The outstanding performance of C_9 N_4 nanosheet could be attributed to the tunable porous structure and electronic structure compatibility.     

三氧化钨表面氢吸附机理的第一性原理研究

采用基于密度泛函理论的第一性原理平面波超软赝势方法,在广义梯度近似下,研究了立方WO_3,WO_3(001)表面结构及其氢吸附机理.计算结果表明立方晶体WO_3理论带隙宽度为0.587 eV.WO_3(001)表面有WO终止(001)表面和O终止(001)表面两种结构,表面结构优化后W—O键长和W—O—W键角改变,从而实现表面弛豫;WO终止(001)表面和O终止(001)表面分别呈现n型半导体特征和p型半导体特征.分别计算了H原子吸附在WO终止(001)表面和O终止(001)表面的H—O_(2c)—H,H—O_(2c)…H—O_(2c),H—O_(1c)—H和H—O_(1c)…H—O_(1c)四种吸附构型,其中H—O_(1c)—H吸附构型的吸附能最小,H—O键最短,H失去电子数最多,分别为-3.684 eV,0.0968 nm和0.55e,此吸附构型最稳定.分析其吸附前后的态密度,带隙从吸附前的0.624 eV增加到1.004 eV,价带宽度基本不变.H的1s轨道电子与O的2p,2s轨道电子相互作用,在-8和-20 eV附近各形成了一个较强的孤立电子峰,两个H原子分别与一个O_(1c)原子形成化学键,最终吸附反应生成了一个H_2O分子,同时产生了一个表面氧空位.