Theoretical Study on the Structural and Electronic Properties of the Reduced SnO_2 (110) Surface

The reduced SnO2（110） surface has been investigated by using first-principles method with a slab model. By examining the vacancy formation energy of three kinds of reduced SnO2（110） surfaces, the most energetically favorable defect surface is confirmed to be the surface with the coexistence of bridging and in-plane oxygen vacancies, which is different with the traditional model by only removing bridging oxygen. The results of band structure calculations indicate that the electronic structure of this defect surface is similar to the SnO surface.

Surface Chemistry and Photochemistry of Cyclohexane on Rutile TiO_(2)(110)

Cyclohexane is a high-valued chemical receivingsignificant interest in liquid hydrogen storage technology.TiO_(2)-based catalysts show high performance in the photocatalytic dehydrogenation of cyclohexane under mild conditions,but the detailed reaction mechanism is not well understood.With the surface science approaches,we have studied the adsorption and surface chemistry of cyclohexane on rutile TiO_(2)(110).The thermal desorption spectroscopy and X-ray photoelectron spectroscopy results both demonstrate the molecular adsorption of cyclohexane on rutile TiO_(2)(110).Upon the UV Hg light irradiation,photodesorption of cyclohexane occurs from both the chemisorbed monolayer and the multilayer.No decomposition nor dehydrogenation of cyclohexane occurs on rutile TiO_(2)(110).These results deepen the fundamental understanding of the surface chemistry of cyclohexane on the TiO_(2)surface.

Electrochemical CO2 reduction over nitrogen-doped SnO2 crystal surfaces

Crystal planes of a catalyst play crucial role in determining the electrocatalytic performance for CO2 reduction.The catalyst SnO2 can convert CO2 molecules into valuable formic acid(HCOOH).Incorporating heteroatom N into SnO2 further improves its catalytic activity.To understand the mechanism and realize a highly efficient CO2-to-HCOOH conversion,we used density functional theory(DFT)to calculate the free energy of CO2 reduction reactions(CO2RR)on different crystal planes of N-doped SnO2(N-SnO2).The results indicate that N-SnO2 lowered the activation energy of intermediates leading to a better catalytic performance than pure SnO2.We also discovered that the N-Sn O2 (211)plane possesses the most suitable free energy during the reduction process,exhibiting the best catalytic ability for the CO2-to-HCOOH conversion.The intermediate of CO2RR on N-SnO2 is HCOO*or COOH* instead of OCHO*.These results may provide useful insights into the mechanism of CO2RR,and promote the development of heteroatomdoped catalyst for efficient CO2RR.

Growth mechanism of palladium clusters on rutile TiO_2 (110) surface

Oxide-supported transition metal systems have been the subject of enormous interest due to the improvement of catalytic properties relative to the separate metal.Thus in this paper,we embark on a systematic study for Pd n （n=1-5） clusters adsorbed on TiO2 （110） surface based on DFT-GGA calculations utilizing periodic supercell models.A single Pd adatom on the defect-free surface prefers to adsorb at a hollow site bridging a protruded oxygen and a five-fold titanium atom along the [110] direction,while Pd dimer is located on the channels with the Pd-Pd bond parallel to the surface.According to the transition states （TSs） search,the adsorbed Pd trimer tends to triangular growth mode,rather than linear mode,while the Pd4 and Pd5 clusters prefer three-dimensional （3D） models.However,the oxygen vacancy has almost no influence on the promotion of Pd n cluster nucleation.Additionally,of particular significance is that the Pd-TiO2 interaction is the main driving force at the beginning of Pd nucleation,whereas the Pd-Pd interaction gets down to control the growth process of Pd cluster as the cluster gets larger.It is hoped that our theoretical study would shed light on further designing high-performance TiO2 supported Pd-based catalysts.

First-Principles Study of Pd Single-Atom Catalysis to Hydrogen Desorption Reactions on MgH2（110） Surface

MgH2 is a promising and popular hydrogen storage material.In this work,the hydrogen desorption reactions of a single Pd atom adsorbed MgH2(110)surface are investigated by using first-principles density functional theory calculations.We find that a single Pd atom adsorbed on the MgH2(110)surface can significantly lower the energy barrier of the hydrogen desorption reactions from 1.802 eV for pure MgH2(110)surface to 1.154 eV for Pd adsorbed MgH2(110)surface,indicating a strong Pd single-atom catalytic effect on the hydrogen desorption reactions.Furthermore,the Pd single-atom catalysis significantly reduces the hydrogen desorption temperature from 573K to 367K,which makes the hydrogen desorption reactions occur more easily and quickly on the MgH2(110)surface.We also discuss the microscopic process of the hydrogen desorption reactions through the reverse process of hydrogen spillover mechanism on the MgH2(110)surface.This study shows that Pd/MgH2 thin films can be used as good hydrogen storage materials in future experiments.

Effects of Surface Defects on Adsorption of CO and Methyl Groups on Rutile TiO_(2)(110)

The interaction of reactants with catalysts has always been an important subject for catalytic reactions.As a promising catalyst with versatile applications,titania has been intensively studied for decades.In this work we have investigated the role of bridge bonded oxygen vacancy(O_(v))in methyl groups and carbon monoxide(CO)adsorption on rutile TiO_(2)(110)(R-TiO_(2)(110))with the temperature programmed desorption technique.The results show a clear different tendency of the desorption of methyl groups adsorbed on bridge bonded oxygen(O_(b)),and CO molecules on the five coordinate Ti^(4+)sites(Ti_(5c))as the Ovconcentration changes,suggesting that the surface defects may have crucial influence on the absorption of species on different sites of R-TiO_(2)(110).

The Ab Initio Studies of NO Chemisorption on TiO_2(110) Surface

The studies of NO chemisorption on TiO2(110) surface are the base of research to NO decomposed to N2O on TiO2 surface. In this paper, 12 kinds of possible models of NO adsorbed on TiO2 perfect and defect surface were calculated by use of ab initio cluster method. We carried out optimization of the geometry, calculation of the chemisorption energy and analysis of the Mulliken population to those adsorption models. According to the calculation results, it can be got that the adsorbed decomposition of NO on defect surface is more advantageous and M6 and M12 are the important models to NO chemisorption and decomposition on TiO2 surface.

氧在SnO_2(110)面吸附机理的研究

用EHMO方法计算了SnO_2(110)面原子簇模型,并计算了表面存在氧空位和氧原子吸附的情况.计算结果表明,表面四配位锡原子是吸附中心,因电子得失而引起的原子净电荷变化是完全定域的.四配位锡原子的净电荷变化很明显,而五配位锡原子吸附的净电荷变化很小.

Conversion of ethanol to acetone &other produces using nano-sensor SnO₂(110): Ab initio DFT

The material considered in this study, SnO2 (110), has a widespread use as gas sensor and oxygen vacancies are known to act as active catalytic sites for the adsorption of small mo-lecules. In the following calculations crystal line SnO2 nano-crystal have been considered. The grains lattice, which has the rutile structure of the bulk material, includes oxygen vacancies and depositing a gaseous molecule, either ethanol, above an atom on the grain surface, generates the adsorbed system. The conduc-tance has a functional relationship with the structure and the distance molecule of the na-no- crystal and its dependence on these quanti-ties parallels the one of the binding energy. The calculations have quantum mechanical detail and are based on a semi-empirical (MNDO me-thod), which is applied to the evaluation of both the electronic structure and of the conductance. We study the structural, total energy, thermo-dynamic and conductive properties of absorp-tion C2H5OH on nano-crystal, which convert to acetaldehyde and acetone.

TiO_2(110)面的弛豫结构及吸附O_2的密度泛函研究

采用DFT/B3LYP方法研究了TiO2 ( 110 )的完整和氧缺陷表面的弛豫构型 ,并对O2 在氧缺陷表面的三种可能吸附构型进行了优化 ,计算了它们的吸附能、振动频率和重叠布居 .分析并预测了吸附后可能产生的物种 .本文的计算结果与XPS 。

SnO_2超微粒非晶薄膜对n-Si光电效应的影响

用等离子激活化学气相沉积（ＰＥＣＶＤ）法制备了ＳｎＯ２超微粒非晶薄膜．Ｘ光电子能谱分析结果表明ＳｎＯ２中的Ｏ／Ｓｎ比超过化学计量比．ｎＳｉ和ＳｎＯ２／ｎＳｉ的表面光电压谱显示，ＳｎＯ２薄膜的处理条件不同，光电压响应所需光强也不同．将ＳｎＯ２薄膜沉积在ｎＳｉ上，可使其光电转换效率提高３个数量级以上，并且也能使ｎＳｉ光电流和光电压有所提高．

SnO_2基电阻薄膜型微氢气传感器的气敏机理

借助Materials Studio中的CASTEP模块,建立了H_2与SnO_2薄膜(110)面的吸附模型。应用基于密度泛函理论(DFT)的第一性原理,确定了H_2在SnO_2(110)面的最佳吸附位置;在此基础上,通过分析H_2在SnO_2(110)面吸附前后态密度(DOS)及表面差分电荷密度的变化,说明了电阻型薄膜型微氢气传感器的微观气敏机理,即当H_2吸附于SnO_2薄膜表面时,薄膜表面电阻减小,其主要原因是H原子的s轨道的部分电子转移到薄膜表面。最后通过灵敏度测试实验,从宏观上对理论分析结果进行了验证。

以工业偏钛酸为原料制备光催化性纳米TiO_2薄膜

以廉价的工业偏钛酸代替了常用的钛酸丁酯为原料在玻璃基体上制备了牢固透明的纳米TiO2 薄膜。扫描探针显微镜 (DFM)观察到TiO2 颗粒的粒径为 2 0～ 30nm。X射线衍射 (XRD)表明 :本研究得到的TiO2 煅烧温度在 5 0 0～ 70 0℃均为稳定的锐钛型。以光降解甲基橙溶液试验检测了TiO2 薄膜的光催化性 ,试验结果表明 :涂层越厚光催化效率越高 ,镀膜 5次时 ,光降解率达到 90 4 5 % ,掺入SnO2 后光降解率由 81 6 8%提高到 91 2 2 % ,薄膜经稀H2 SO4处理后光降解率由 81 6 8%提高到 88 31%。

Synthesis of Cr-Al_2O_3 Cermet Selective Surfaces Coated by SnO_2 Thin Film by Air Plasma Spraying

High efficient Cr-Al2O3 cermet selective surfaces coated by sol-gel SnO2 thin film for high-temperature application were synthesized by air plasma spraying(APS),followed further heat and polish treatment.The phase composition and micro morphology of coating samples were characterized by X-ray diffractions(XRD),scanning electron microscope(SEM)and roughmeter respectively.The solar absorptance(α)and thermal emittance(ε)were determined by optical spectrum instrument.The results show that Cr-Al2O3 cermet coating has a high absorptivity nearly 0.90.But unfortunately,the emissivity of these coatings is nearly 0.50 because of the big thickness and coarse surface prepared by APS technique.However,once coated SnO2 thin film,the composite coatings exhibit excellent selective absorbing property of α=0.89 and ε=0.12.Thus,SnO2 thin film plays a significant role in decreasing the emissivity of coatings as antireflection layer.And furthermore,the optical performance shows that more metal content and smooth surface are favorable for the selective absorbing property.Moreover,the coatings have excellent bond strength with stainless steel substrate and thermal shock resistance at high temperature.

Stochastic resonance in surface catalytic oxidation of carbon monoxide induced by colored noise

The dynamical behavior of surface catalytic oxidation reaction of Pt(110)/CO+O2 modulated by colored noise, under the condition of specific temperature, has been investigated when the partial pressure of CO gas is near the supercritical Hopf bifurcation point. By computer simulation the oscillation and stochastic resonance induced by colored noise are observed. The influences of the intensity and correlation time of colored noise on stochastic resonance are discussed. The range of sensitivity of the system to the environmental fluctuation is analyzed.

Chlorine-modified SnO2 electron transport layer for high-efficiency perovskite solar cells

A high-quality electron transport layer(ETL)is a critical component for the realization of high-efficiency perovskite solar cells.We developed a controllable direct-contact reaction process to prepare a chlorinated SnO2(SnO2-Cl)ETL.It is unique in that(a)102-dichlorobenzene is used to provide more reactive Cl radicals for more in-depth passivation;(b)it does not introduce any impurities other than chlorine.It is found that the chlorine modification significantly improves the electron extraction.Consequently,its associated solar cell efficiency is increased from 17.01%to 17.81%comparing to the pristine SnO2 ETL without the modification.The hysteresis index is significantly reduced to 0.017 for the SnO2-Cl ETL.

Electrochemical performance of a nano SnO_2-modified LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 cathode material

The nano SnO2-modified LiNi1/3Co1/3Mn1/3O2 was successfully prepared by a carrier transfer method. The pristine and modified samples were characterized with various techniques such as XRD, SEM, XPS and EDS. The results showed that the SnO2particles did not enter the crystal structure of LiNi1/3Co1/3Mn1/3O2, many nano SnO2 particles were uniformly covered on the surface of LiNi1/3Co1/3Mn1/3O2 and the modified thin layer could inhibit the dissolution of transition metal oxides. The electrochemical tests indicated that the existence of nano SnO2 could improve the discharge capacity and rate capability owing to the decreased interfacial polarization, The cycling stability was remarkably improved at room temperature and 55 ℃. The XRD patterns of the fresh NCM electrode and after 50 cycles proved that the structural change of NCM was not so effective on the capacity fade.

Chemical Investigation of the NO_x Detection Mechanisms by Semiconductor Metal Oxide Nanoparticles

This work reports an FTIR study of the NO_x adsorption/desorption cycles on tin oxide nanosized particles under the operating conditions of real sensors (150℃,in presence of O_2).The chemical reactions are monitored in situ and correlated with the variations of the SnO_2 electrical conductivity.On the basis of the FTIR spectra,two contributing mechanisms for the NO_x detection are suggested.The first one presents the formation of bridged nitrate groups bound to the SnO_2 surface via oxygen vacancies acting as electron donor sites.The second mechanism also involves surface oxygen vacancies in the coordination of NO_x,but this time the formation of NO_x anionic species is considered.Both mechanisms lead to the decrease of the electrical conductivity under NO_x adsorption.However,the bridged nitrate groups are not reversible under gas desorption and thus irreversibly contaminate the surface after the first NO_x adsorption.On the contrary,the nitrosyl anionic species are reversible and,from the second NO_x adsorption/desorption cycle,ensure the reproducibility of the sensor response.

Texture ZnO Thin-Films and their Application as Front Electrode in Solar Cells

In this paper, three kinds of textured ZnO thin-films (the first kind has the textured structure with both columnar and polygon, the second posses pyramid-like textured structure only, and the third has the textured structure with both crater-like and pyramid-like), were prepared by three kinds of methods, and the application of these ZnO thin-films as a front electrode in solar cell was studied, respectively. In the first method with negative bias voltage and appropriate sputtering parameters, the textured structure with columnar and polygon on the surface of ZnO thin-film are both existence for the sample prepared by direct magnetron sputtering. Using as a front electrode in solar cell, the photoelectric conversion efficiency Eff of 7.00% was obtained. The second method is that by sputtering on the ZnO:Al self-supporting substrate, and the distribution of pyramid-like was gained. Moreover, the higher (8.25%) photoelectric conversion efficiency of solar cell was got. The last method is that by acid-etching the as-deposited ZnO thin-film which possesses mainly both columnar and polygon structure, and the textured ZnO thin-film with both crater-like and pyramid-like structure was obtained, and the photoelectric conversion efficiency of solar cell is 7.10% when using it as front electrode. These results show that the textured ZnO thin-film prepared on self-supporting substrate is more suitable for using as a front electrode in amorphous silicon cells.

Unique adsorption behaviors of NO and O_2 at hydrogenated anatase TiO_2(101)

Titanium dioxide（TiO2） is one of the most widely studied transition metal oxides, especially for its unique performances in heterogeneous photocatalysis. Different phases of TiO2 have been found to exhibit different photo-activities, though the origins are still not fully understood. In this work, we use the density functional theory（DFT） calculations, corrected by on-site Coulomb and long-range dispersion interactions, to study the adsorptions of nitric oxide（NO） and oxygen（O2） molecules on the clean and hydrogenated anatase TiO2（101） surfaces. We also compare the detailed calculated results regarding their structural, energetic and electronic properties with those obtained at rutile TiO2（110）. It has been found that the behaviors of the surface localized electrons being transferred from adsorbed H, as well as the adsorption behaviors of NO and O2 are quite different at the two surfaces, which can be attributed to their characteristic local bonding structures around the surface hydroxyl. These results may also help explain the different photocatalytic activities of these two main facets of anatase and rutile TiO2