Solid‐State NMR and DFT Combined for the Surface Study of Functionalized Silicon Nanoparticles

Silicon nanoparticles (NPs) serve a wide range of optical, electronic, and biological applications. Chemical grafting of various molecules to Si NPs can help to passivate their reactive surfaces, “fine‐tune” their properties, or even give them further interesting features. In this work, ¹H, ¹³C, and ²⁹Si solid‐state NMR spectroscopy has been combined with density functional theory calculations to study the surface chemistry of hydride‐terminated and alkyl‐functionalized Si NPs. This combination of techniques yields assignments for the observed chemical shifts, including the contributions resulting from different surface planes, and highlights the presence of physisorbed water. Resonances from near‐surface ¹³C nuclei were shown to be substantially broadened due to surface disorder and it is demonstrated that in an ambient environment hydride‐terminated Si NPs undergo fast back‐bond oxidation, whereas long‐chain alkyl‐functionalized Si NPs undergo slow oxidation. Furthermore, the combination of NMR spectroscopy and DFT calculations showed that the employed hydrosilylation reaction involves anti‐Markovnikov addition of the 1‐alkene to the surface of the Si NPs.     

Designed Single‐Step Synthesis,Structure, and Derivative Textural Properties of Well‐Ordered Layered Penta‐coordinate Silicon Alcoholate Complexes

The controllable synthesis of well‐ordered layered materials with specific nanoarchitecture poses a grand challenge in materials chemistry. Here the solvothermal synthesis of two structurally analogous 5‐coordinate organosilicate complexes through a novel transesterification mechanism is reported. Since the polycrystalline nature of the intrinsic hypervalent Si complex thwarts the endeavor in determining its structure, a novel strategy concerning the elegant addition of a small fraction of B species as an effective crystal growth mediator and a sacrificial agent is proposed to directly prepare diffraction‐quality single crystals without disrupting the intrinsic elemental type. In the determined crystal structure, two monomeric primary building units (PBUs) self‐assemble into a dimeric asymmetric secondary BU via strong Na⁺?O^2? ionic bonds. The designed one‐pot synthesis is straightforward, robust, and efficient, leading to a well‐ordered (10ī)‐parallel layered Si complex with its principal interlayers intercalated with extensive van der Waals gaps in spite of the presence of substantial Na⁺ counter‐ions as a result of unique atomic arrangement in its structure. However, upon fast pyrolysis, followed by acid leaching, both complexes are converted into two SiO₂ composites bearing BET surface areas of 163.3 and 254.7 m² g^?1 for the pyrolyzed intrinsic and B‐assisted Si complexes, respectively. The transesterification methodology merely involving alcoholysis but without any hydrolysis side reaction is designed to have generalized applicability for use in synthesizing new layered metal–organic compounds with tailored PBUs and corresponding metal oxide particles with hierarchical porosity.     

Mesoporous Amorphous Silicon: A Simple Synthesis of a High‐Rate and Long‐Life Anode Material for Lithium‐Ion Batteries

Amorphous Si (a‐Si) shows potential advantages over crystalline Si (c‐Si) in lithium‐ion batteries, owing to its high lithiation potential and good tolerance to intrinsic strain/stress. Herein, porous a‐Si has been synthesized by a simple process, without the uses of dangerous or expensive reagents, sophisticated equipment, and strong acids that potential cause environment risks. These porous a‐Si particles exhibit excellent electrochemical performances, owing to their porous structure, amorphous nature, and surface modification. They deliver a capacity of 1025 mAh g^?1 at 3 A g^?1 after 700 cycles. Moreover, the reversible capacity after electrochemical activation, is quite stable throughout the cycling, resulting in a capacity retention about around 88 %. The direct comparison between a‐Si and c‐Si anodes clearly supports the advantages of a‐Si in lithium‐ion batteries.     

Stable Immobilization of Nickel Ions on Covalent Organic Frameworks for Panchromatic Photocatalytic Hydrogen Evolution

Post-coordination design on covalent organic frameworks (COFs) is an efficient strategy for elevating the photocatalytic activity of organic moiety. However, the rigid skeletons and densely layered stacking of two-dimensional (2D) COFs cannot be flexibly adapted for specific conformations of metal complexes, thereby impairing the metal-COF cooperation. Here, we adopt a solvothermal method to immobilize nickel(II) ions into a 2,2′-bipyridine-containing 2D COF, forming a stable coordination motif. Such the complex remarkably enhances the photocatalytic performance, giving an optimized H₂ evolution rate of as high as 51 300 μmol h⁻¹ g⁻¹, 2.5 times higher than the pristine COF. The evolved hydrogen gas can also be detected upon 700-nm light irradiation, while its analog synthesized by the traditional coordination method is photo-catalytically inert. This work provides a strategy for optimizing the metal-COF coordination system and strengthening a synergy for electronic regulation in photocatalysis.     

Diamondoids approach to electronic,structural, and vibrational properties of GeSi superlattice nanocrystals: a first-principles study

Germanium silicide diamondoids are used to determine electronic, structural, and vibrational properties of GeSi superlattice nanocrystals and bulk as their building block limit. Density functional theory at the generalized gradient approximation level of Perdew, Burke, and Ernzerhof (PBE) with 6-31G(d) basis including polarization functions is used to investigate the electronic structure of these diamondoids. The investigated molecules and diamondoids range from GeSiH₆ to Ge₆₃Si₆₃H₉₂. The variation of the energy gap is shown from nearly 7 eV toward bulk value which is slightly higher than the average of Si and Ge energy gaps. Variations of bond lengths, tetrahedral, and dihedral angles as the number of atoms increases are shown taking into account the effect of shape fluctuations. Localized and delocalized electronic charge distribution and bonds for these molecules are discussed. Vibrational radial breathing mode (RBM) converges from its initial molecular value at 332 cm^?1 to its bulk limit at 0 cm^?1 (blue shift). Longitudinal optical-highest reduced mass mode (HRMM) converges from its initial molecular value 332 cm^?1 to experimental bulk limit at 420.7 cm^?1 (red shift). Hydrogen vibrational modes are nearly constant in their frequencies as the size of diamondoids increases in contrast with lower frequency Ge–Si vibrational modes. GeSi diamondoids can be identified from surface hydrogen vibrational modes fingerprint, while the size of these diamondoids can be identified from Ge–Si vibrational modes.     

Selective attachment of benzaldehyde on Si(100)-2 x 1: structure, selectivity, and mechanism

The interaction of benzaldehyde with the Si(100) surface has been investigated as a model system for understanding the interaction of conjugated pi-electron systems with semiconductor surfaces. Vibrational features of chemisorbed benzaldehyde unambiguously demonstrate that the carbonyl group directly interacts with the Si surface dangling bonds, evidenced in the disappearance of the C=O stretching mode around 1713 cm(-1) coupled with the retention of all vibrational signatures of its phenyl ring. X-ray photoemission spectroscopy shows that both C 1s and O 1s binding energies of the carbonyl group display large downshifts by 1.9 and 1.3 eV, respectively. Vibrational and electronic results show that the covalent attachment of benzaldehyde on Si(100) occurs in a highly selective manner through the direct interaction of both C and O atoms of the carbonyl group with a Si=Si dimer to form a four-membered Si-C-O-Si ring at the interface, leaving a nearly unperturbed phenyl ring protruding into vacuum. This conclusion is further confirmed by the observation of a predominant protrusion for benzaldehyde adsorbed on Si(100)-2 x 1 in scanning tunneling microscopy experiments, consistent with the predication of density-functional theory calculation.     

Investigation of 500 keV Si ion induced surface structuring of Ni and Ti for enhancement of field emission properties

The present paper reports the investigation of surface morphology, elemental composition, phase changes and field emission properties of Si ion irradiated nickel (Ni) and titanium (Ti). The Ni and Ti targets have been irradiated with 500 keV Si ions generated by Pelletron accelerator at various fluences ranging from 6.9 × 10¹³ to 77.1 × 10¹³ ions/cm². Stopping range of ions in matter analysis revealed higher values of electronic stopping and sputtering yield for Ni as compared with Ti. For both irradiated metals, electronic energy loss dominant over the nuclear stopping. The growth of induced surface structures have been analysed by using field emission scanning electron microscopy (FESEM) analysis. In case of Ni, as the ion fluence increases from 6.9 × 10¹³ to 65.8 × 10¹³ ions/cm², the formation of spherical particulates, agglomers and sputtering is observed. Although in the case of Ti, with the increase of Si ion fluence from 11.6 × 10¹³ to 77.1 × 10¹³ ions/cm², the formation of irregular-shaped particulates along with crater and sputtered channels is observed. X-ray diffraction (XRD) analysis shows that no new phase is identified. However, a significant increase in peak intensity is observed with increasing ion fluence. The variation in crystallite size and dislocation line density is also observed as a function of Si ion fluence. Fourier transform infrared spectroscopy analysis shows that no bands are formed after the Si ion irradiation. Field emission properties of ion-structured Ni and Ti are well correlated with the growth of surface structures observed by SEM and dislocation line density evaluated by XRD analysis.     

Synthesis and Hydrogen-Bond Patterns of Aryl-Group Substituted Silanediols and -triols from Alkoxy- and Chlorosilanes

Organosilanols typically show a high condensation tendency and only exist as stable isolable molecules under very specific steric and electronic conditions at the silicon atom. In the present work, various novel representatives of this class of compounds were synthesized by hydrolysis of alkoxy- or chlorosilanes. Phenyl, 1-naphthyl, and 9-phenanthrenyl substituents at the silicon atom were applied to systematically study the influence of the aromatic substituents on the structure and reactivity of the compounds. Chemical shifts in ²⁹Si NMR spectroscopy in solution, correlated well with the expected electronic situation induced by the substitution pattern on the Si atom. ¹H NMR studies allowed the detection of strong intermolecular hydrogen bonds. Single-crystal X-ray structures of the alkoxides and the chlorosilanes are dominated by π-π interactions of the aromatic systems, which are substituted by strong hydrogen bonding interactions representing various structural motifs in the respective silanol structures.     

Comparison of solar silicon feedstock

One of the major factors in reducing a cost of commercial solar cells is the lifetime of the photovoltaic material. In this work, a deterioration of Si generated by solvent metal gathering method (SMG) and Si removed from damaged solar cells is analyzed and compared with electronic grade Si. The differences in heating and cooling cycles on the DTA curves of different solar grade Si and Cu–Si mixtures are compared. A nonequilibrium exothermic reaction in Si generated by SMG method is recorded in samples aged in room atmosphere for 1 year. The outcomes of the cooling cycles after the DTA analyses for various solar grades Si were not significantly differentiated from the referred electronic grade Si indicating that recrystallization of aged Si diminishes the problem related to agglomeration of Cu and oxygen on the surface of Si solar grade particles. The DTA tests showed that recrystallized Si from the deteriorated solar cells can be recycled as feedstock materials for solar cells applications while Si generated by SMG method can be used for blending in order to achieve a long lifetime of Si solar cells.     

On copper diffusion in silicon measured by glow discharge mass spectrometry

Copper contamination occurs frequently in silicon for photovoltaic applications due to its very fast diffusion coupled with a low solid solubility, especially at room temperature. The combination of these properties exerts a challenge on the direct analysis of Cu bulk concentration in Si by sputtering techniques like glow discharge mass spectrometry (GDMS). This work aims at addressing the challenges in quantitative analysis of fast diffusing elements in Si matrix by GDMS. N-type, monocrystalline (Czochralski) silicon samples were intentionally contaminated with Cu after solidification and consequently annealed at 900 °C to ensure a homogeneous distribution of Cu in the bulk. The samples were quenched after annealing to control the extent of the diffusion to the surface prior to the GDMS analyses, which were carried out at different time intervals from within few minutes after cooling onward. The Cu profiles were measured by high-resolution GDMS operating in a continuous direct current mode, where the integration step length was set to ～0.5 μm over a total sputtered depth of 8–30 μm. The temperature of the samples during the GDMS analyses was also measured in order to evaluate the diffusion. The Cu contamination of n-type Si samples was observed to be highly material dependent. The practical impact of Cu out-diffusion on the calculation of the relative sensitivity factor (RSF) of Cu in Si is discussed.     

改善SBA-15介孔材料水热稳定性的简单溶剂热后处理方法

提出了一种有效改善SBA-15介孔材料水热稳定性的简单溶剂热后处理方法. SBA-15材料经环己烷、甲苯和正丁醇等有机溶剂在157和190 oC密闭容器中分别处理6–24 h后,可呈现很好的水热稳定性.它们在800 oC经100%水蒸气处理12 h,依然能保持很好的有序介孔结构,比表面积可高达192–281 m2/g.其中,经环己烷190 oC溶剂热处理24 h的样品表现出最优的水热稳定性.溶剂热处理能显著提升材料孔壁中类似Si(OSi)2(OH)2和Si(OSi)3OH结构的Si–OH基间脱水,形成稳定的Si(OSi)4结构,从而有效减少了SBA-15材料孔壁的缺陷.由此,介孔材料的水热稳定性得到明显改善.溶剂热处理对SBA-15材料水热稳定性的这种提升作用与所用溶剂性质、处理温度以及SBA-15前驱体的类型密切相关.其中,以低沸点的非极性溶剂处理焙烧后的SBA-15材料表现出最好的稳定化效果.该方法具有简单、低能耗的特点,其在制备高水热稳定的有序硅基介孔材料上有很好的潜在应用价值.     

t-Si64: A Novel Silicon Allotrope

Utilizing first principle calculations, a novel Si₆₄ silicon allotrope in the I4₁/amd space group with tetragonal symmetry (denoted as t-Si₆₄ below) is proposed in this work. In addition, also its structural, anisotropic mechanical, and electronic properties along with its minimum thermal conductivity κ_min were predicted. The mechanical and thermodynamic stability of t-Si₆₄ were evaluated by means of elastic constants and phonon spectra. The electronic band structure indicates that t-Si₆₄ is an indirect band gap semiconductor with a band gap: 0.67 eV (primitive cell) compared to a direct band gap of 0.70 eV with respect to a conventional cell. The minimum thermal conductivity of t-Si₆₄ (0.74 W cm⁻¹ K⁻¹) is much smaller than that of diamond silicon (1.13 W cm⁻¹ K⁻¹). Therefore, Si−Ge alloys in the I4₁/amd space group are potential thermoelectric materials.     

锂离子电池负极Si@LiAlO2纳米复合材料的简易制备(英文)

采用溶剂热法和煅烧法制备了LiAlO₂包覆Si纳米颗粒(Si@LiAlO₂)的复合材料。Si@LiAlO₂纳米颗粒具有开口和通道的树枝状结构。电化学性能测试表明,其在100 mA·g^-1电流密度下循环100次后可逆容量为364.1 mAh·g^-1。纳米复合材料的树枝状结构使其具有优越的循环性能。在树枝状结构中,纳米尺度的硅颗粒缩短了锂离子的传输路径,LiAlO₂包覆层、孔隙和开口缓冲了硅在充放电过程中的体积变化。     

Adaptation of a commercial total reflection X-ray fluorescence system for wafer surface analysis equipped with a new generation of silicon drift detector

Within the framework of a collaborative project, it is shown that commercial total reflection X-ray fluorescence (TXRF) systems used in laboratories can easily be upgraded with a silicon drift detector (SDD). SDDs have advantages when used with fully automatized wafer analyzers working under cleanroom conditions, because no liquid nitrogen is required as they are electrically cooled. The goal of this work was the integration of a KETEK 10 mm² SDD in an ATOMIKA 8030W wafer analyzer with special attention to maintain the high degree of automation of the system. An electronic device was designed to establish communication between the SDD and the TXRF electronic control system. The adapted system was tested and compared with the original setup using an 80 mm² Si(Li) detector. Multielement droplet samples on silicon wafers were analyzed and the results showed two times better detection limits for the Si(Li) detector for 1000 pg Ni in comparison to the SDD. Additionally, a RADIANT 50 mm² SDD (VORTEX) was tested which showed identical detection limits compared to the 80 mm² Si(Li) detector.     

Synthesis and Study of Plasmon‐Induced Carrier Behavior at Ag/TiO2 Nanowires

Nanocomposites of Ag/TiO₂ nanowires with enhanced photoelectrochemical performance have been prepared by a facile solvothermal synthesis of TiO₂ nanowires and subsequent photoreduction of Ag⁺ ions to Ag nanoparticles (AgNPs) on the TiO₂ nanowires. The as‐prepared nanocomposites exhibited significantly improved cathodic photocurrent responses under visible‐light illumination, which is attributed to the local electric field enhancement of plasmon resonance effect near the TiO₂ surface rather than by the direct transfer of charge between the two materials. The visible‐light‐driven photocatalytic performance of these nanocomposites in the degradation of methylene blue dye was also studied, and the observed improvement in photocatalytic activity is associated with the extended light absorption range and efficient charge separation due to surface plasmon resonance effect of AgNPs.     

Silaacetylene: A possible target for experimental studies

The equilibrium geometries and transition states for interconversion of the CSiH₂ isomers in the singlet electronic ground state are optimized at the MP2 and CCSD(T) levels of theory using a TZ2P basis set. The heats of formation, vibrational frequencies, infrared intensities, and rotational constants are also predicted. There are three energy minima on the CSiH₂ potential energy surface. Energy calculations at CCSD(T)/TZ2P(fd) + ZPE predict that the global energy minimum is silavinylidene (1), which is 34.1 kcal mol⁻¹ lower in energy than trans-bent silaacetylene (2) and 84.1 kcal mol⁻¹ more stable than the vinylidene isomer (3). The barrier for rearrangement 2→1 is calculated at the same level of theory to be 5.1 kcal mol⁻¹, while for the rearrangement 3→2 a barrier of 2.7 kcal mol⁻¹ is predicted. The natural bond orbital (NBO) population scheme indicates a clear polarization of the C(SINGLE BOND)Si bonds toward the carbon end. A significant ionic contribution to the C(SINGLE BOND)Si bonds of 1 and 2 is suggested by the NBO analysis. The C(SINGLE BOND)Si bond length of trans-bent silaacetylene (2) is longer than previously calculated [1.665 Å at CCSD(T)/TZ2P)]. The calculated carbon-silicon bond length of 2 is in the middle between the C(SINGLE BOND)Si double bond length of 1 (1.721 Å) and the C(SINGLE BOND)Si triple bond of the linear form HCSiH (4), which is 1.604 Å. Structure 4 is a higher-order saddle point on the potential energy surface. © 1996 by John Wiley & Sons, Inc.     

Labeling and Probing the Silica Surface Using Mechanochemistry and 17O NMR Spectroscopy**

In recent years, there has been increasing interest in developing cost-efficient, fast, and user-friendly ¹⁷O enrichment protocols to help to understand the structure and reactivity of materials by using ¹⁷O NMR spectroscopy. Here, we show for the first time how ball milling (BM) can be used to selectively and efficiently enrich the surface of fumed silica, which is widely used at industrial scale. Short milling times (up to 15 min) allowed modulation of the enrichment level (up to ca. 5 %) without significantly changing the nature of the material. High-precision ¹⁷O compositions were measured at different milling times by using large-geometry secondary-ion mass spectrometry (LG-SIMS). High-resolution ¹⁷O NMR analyses (including at 35.2 T) allowed clear identification of the signals from siloxane (Si−O−Si) and silanols (Si−OH), while DNP analyses, performed by using direct ¹⁷O polarization and indirect ¹⁷O{¹H} CP excitation, agreed with selective labeling of the surface. Information on the distribution of Si−OH environments at the surface was obtained from 2D ¹H−¹⁷O D-HMQC correlations. Finally, the surface-labeled silica was reacted with titania and using ¹⁷O DNP, their common interface was probed and Si−O−Ti bonds identified.     

The constructing of Si-Fe-Sn co-solution surface of composite iron oxide catalyst via vapor methanol pretreatment and application in gaseous phenolic alkylation

Iron oxide catalysts which were used in gaseous 2,5-dimethylphenol (2,5-DMP) alkylation with methanol was modified by Sn, Si and K to produce 2,3,6-trimethylphenol (2,3,6-TMP). Characterized by FE-SEM, ICP-OES, XRD, Raman, in-situ FT-IR, N₂-adsorption/desorption, XPS, FE-TEM and NH₃-TPD. The primary surface segregated SnO₂ nanocrystals and the amorphous Si-containing coordination structures which were formed on non-activated catalyst limited the growth of hematite grains; catalysts activation triggered by vapor methanol successfully formed a surface Si-Fe-Sn ternary co-solution structure through lattice oxygen consumption and migration, which passivated the uniformity of grains and blocked the direct contact between them; K was used to weaken the acidity of undesirable strong acid sites. The main product was proved to be 2,3,6-TMP by ¹H NMR, which is a synthetic intermediate of vitamin E with high value. The best 2,5-DMP conversion and 2,3,6-TMP selectivity can reach 99.25% and 100% under the condition of 370 °C and 1.5 h⁻¹ LHSV, respectively. Compared with traditional iron oxide catalysts, the undesirable sintering has been reduced by 23.2% and 2,3,6-TMP productivity is 1.5 times that of the reference data because of this structure. This work provides a good reference for the improvement of other iron-based materials used in complex reductive atmosphere.     

Chemical surface passivation of 3C‐SiC nanocrystals: A first‐principle study

The effect of the chemical surface passivation, with hydrogen atoms, on the energy band gap of porous cubic silicon carbide (PSiC) was investigated. The pores are modeled by means of the supercell technique, in which columns of Si and/or C atoms are removed along the [001] direction. Within this supercell model, morphology effects can be analyzed in detail. The electronic band structure is performed using the density functional theory based on the generalized gradient approximation. Two types of pores are studied: C‐rich and Si‐rich pores surface. The enlargement of energy band gap is greater in the C‐rich than Si‐rich pores surface. This supercell model emphasizes the interconnection between 3C‐SiC nanocrystals, delocalizing the electronic states. However, the results show a clear quantum confinement signature, which is contrasted with that of nanowire systems. The calculation shows a significant response to changes in surface passivation with hydrogen. The chemical tuning of the band gap opens the possibility plenty applications in nanotechnology. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110:2455–2461, 2010     

A protophilic solvent‐assisted solvothermal approach to Cu‐BTC for enhanced CO2 capture

Cu‐BTC–ethylenediamine (EDA)/polyethyleneimine (PEI) adsorbents were synthesized using a protophilic solvent‐assisted solvothermal method. EDA was introduced to enhance the degree of activation due to its lower boiling point allowing it to be removed easily compared with dimethylformamide. A contrast experiment was done by introducing PEI to the solvothermal solution considering its higher boiling point. Powder X‐ray diffraction, scanning electron microscopy and Raman spectroscopic characterizations were performed to investigate the effect of EDA/PEI on crystallinity and morphology of the adsorbents. ¹H NMR characterization and elemental analysis were performed to study the removal rate of organic guest molecules and the degree of activation. Nitrogen physical adsorption and CO₂ adsorption isotherms were used to measure the surface area and CO₂ adsorption capacities. The CO₂ adsorption mechanism of the synthesized adsorbents is mainly dependent on physisorption determined by surface area. Furthermore, open metal sites generated by the enhancement of degree of activation also promote the CO₂ adsorption performance. Therefore, adsorbents synthesized using the protophilic solvent‐assisted solvothermal method exhibit excellent CO₂ adsorption performance. Copyright © 2015 John Wiley & Sons, Ltd.