Differentiating between Acidic and Basic Surface Hydroxyls on Metal Oxides by Fluoride Substitution: A Case Study on Blue TiO2 from Laser Defect Engineering

Both oxygen vacancies and surface hydroxyls play a crucial role in catalysis. Yet, their relationship is not often explored. Herein, we prepare two series of TiO₂ (rutile and P25) with increasing oxygen deficiency and Ti³⁺ concentration by pulsed laser defect engineering in liquid (PUDEL), and selectively quantify the acidic and basic surface OH by fluoride substitution. As indicated by EPR spectroscopy, the laser-generated Ti³⁺ exist near the surface of rutile, but appear to be deeper in the bulk for P25. Fluoride substitution shows that extra acidic bridging OH are selectively created on rutile, while the surface OH density remains constant for P25. These observations suggest near-surface Ti³⁺ are highly related to surface bridging OH, presumably the former increasing the electron density of the bridging oxygen to form more of the latter. We anticipate that fluoride substitution will enable better characterization of surface OH and its correlation with defects in metal oxides.     

Photosynthesis of Benzonitriles on BiOBr Nanosheets Promoted by Vacancy Associates

Photocatalytic organic functionalization reactions represent a green, cost-effective, and sustainable synthesis route for value-added chemicals. However, heterogeneous photocatalysis is inefficient in directly activating ammonia molecules for the production of high-value-added nitrogenous organic products when compared with oxygen activation in the formation of related oxygenated compounds. In this study, we report the heterogeneous photosynthesis of benzonitriles by the ammoxidation of benzyl alcohols (99 % conversion, 93 % selectivity) promoted using BiOBr nanosheets with surface vacancy associates. In contrast, the main reaction of catalysts with other types of vacancy sites is the oxidation of benzyl alcohol to benzaldehyde or benzoic acid. Experimental measurements and theoretical calculations have demonstrated a specificity of vacancy type with respect to product selectivity, which arises from the adsorption and activation of NH₃ and O₂ that is required to promote subsequent C−N coupling and oxidation to nitrile. This study provides a better understanding of the role of vacancies as catalytic sites in heterogeneous photocatalysis.     

Breaking Surface Atomic Monogeneity of Rh2P Nanocatalysts by Defect-Derived Phosphorus Vacancies for Efficient Alkaline Hydrogen Oxidation

Breaking atomic monogeneity of catalyst surfaces is promising for constructing synergistic active centers to cope with complex multi-step catalytic reactions. Here, we report a defect-derived strategy for creating surface phosphorous vacancies (P-vacancies) on nanometric Rh₂P electrocatalysts toward drastically boosted electrocatalysis for alkaline hydrogen oxidation reaction (HOR). This strategy disrupts the monogeneity and atomic regularity of the thermodynamically stable P-terminated surfaces. Density functional theory calculations initially verify that the competitive adsorption behavior of H_ad and OH_ad on perfect P-terminated Rh₂P{200} facets (p-Rh₂P) can be bypassed on defective Rh₂P{200} surfaces (d-Rh₂P). The P-vacancies enable the exposure of sub-surface Rh atoms to act as exclusive H adsorption sites. Therein, the H_ad cooperates with the OH_ad on the peripheral P-sites to effectively accelerate the alkaline HOR. Defective Rh₂P nanowires (d-Rh₂P NWs) and perfect Rh₂P nanocubes (p-Rh₂P NCs) are then elaborately synthesized to experimentally represent the d-Rh₂P and p-Rh₂P catalytic surfaces. As expected, the P-vacancy-enriched d-Rh₂P NWs catalyst exhibits extremely high catalytic activity and outstanding CO tolerance for alkaline HOR electrocatalysis, attaining 5.7 and 14.3 times mass activity that of p-Rh₂P NCs and commercial Pt/C, respectively. This work sheds light on breaking the surface atomic monogeneity for the development of efficient heterogeneous catalysts.     

Frenkel‐Defect‐Mediated Chemical Ordering Transition in a Li–Mn–Ni Spinel Oxide

Using spinel‐type Li(Mn_1.5Ni_0.5)O₄ with two different cations, Mn and Ni, in the oxygen octahedra as a model system, we show that a cation ordering transition takes place through the formation of Frenkel‐type point defects. A series of experimental results based on atomic‐scale observations and in situ powder diffractions along with ab initio calculations consistently support such defect‐mediated transition behavior. In addition to providing a precise suggestion of the intermediate transient states and the resulting kinetic pathway during the transition between two phases, our findings emphasize the significant role of point defects in ordering transformation of complex oxides.     

Unoccupied titanium 3d states due to subcluster formation in stoichiometric TiO2 nanoparticles

The source of unoccupied Ti 3d states in the case of stoichiometric anatase structured (TiO₂)_n clusters has been investigated using ab initio methods. These unoccupied gap states appear for example in the case of a stoichiometric (TiO₂)₃₈ cluster. We show that the origin of these gap states is related to effective subcluster formation which gives rise to empty defect‐like gap states, when these states are split off from conduction band. © 2015 Wiley Periodicals, Inc.     

ZnO‐Coated Carbon Nanotubes: Inter‐Diffusion of Carboxyl Groups and Enhanced Photocurrent Generation

ZnO is a defect‐governed oxide and emits light at both visible and UV regimes. This work employs atomic layer deposition to produce oxide particles on oxygenated carbon nanotubes, and the composites only show emission profiles at short wavelengths. The quenching of defect‐related emissions at long wavelengths is verified, owing to carboxyl diffusion into oxygen vacancies, and doping is supported by ZnCO₃ formation in oxide lattice. Fully coated tubes display an increased photocurrent and the quantum efficiency increases by 22 % relative to the bare nanotubes.     

双功能改性的T型分子筛膜用于有机溶剂脱水

将3-氨丙基三乙氧基硅烷（APTES）引入到T型分子筛膜表面,用以修饰多晶膜合成过程中产生的缺陷。X射线衍射、场发射扫描电子显微镜、X射线光电子能谱和FT-IR等方法的表征结果显示,APTES通过“键合”的形式被成功地修饰到膜表面上。APTES层起到2个作用：一是提高膜的亲水性;二是减少膜层的缺陷。将修饰后的膜应用在348 K、90%的异丙醇水溶液的脱水时,该膜表现出比较高的分离因子和通量。该方法重复性良好,5个修饰后的膜样品的选择性平均增加了大约8倍（从359±23增加到2 934±183）,而渗透通量仅仅从（3.52±0.10） kg·m^-2·h^-1降低到（3.06±0.14） kg·m^-2·h^-1（减少13.07%）。在363 K下,修饰的膜经过100 h的连续测试,膜渗透测得的水含量均可达到99.50%以上,表明修饰后的膜性能较稳定。     

Progress in fluorene-based wide-bandgap steric semiconductors

Molecular bulks are favorable for the thermal and morphological stability in organic wide-bandgap semiconducting polymers with potential applications in both information and energy electronics. In this review, we present our progress in the design of fluorene-based bulky semiconductors with a fractal four-element pattern. Firstly, we established one-pot methods to spirofluorenes, especially spiro[fluorene-9,9′-xanthene](SFX) serving as the next-generation spiro-based semiconductors. Secondly, we observed the supramolecular forces at the bulky groups and discovered the supramolecular steric hindrance(SSH) effect on polymorphisms, nanocrystals as well as device performance. Thus, a synergistically molecular attractor-repulsor theory(SMART) was proposed for the control of nanocrystal morphology, thin film phase and morphology. Thirdly, the third possible type of defects has been identified to generate green band(g-band) emission in widebandgap semiconductors by the introduction of molecular strain design of cyclofluorene. Finally, the first bulky polydiarylfluorene with highly crystalline and β conformation was achieved by an attractor-repulsor design of tadpole-shape monomer, which offered an effective platform to fabricate stable wide-bandgap semiconducting devices. All the discoveries offer the solid basis to break through bottlenecks of organic/polymer wide-bandgap semiconductors by the improvements of overall performances.     

Nematodynamics and structures in junctions of cylindrical micropores

ABSTRACT

We explore equilibrium structures and flow-driven deformations of nematic liquid crystals confined to 3D junctions of cylindrical micropores with homeotropic surface anchoring. The topological state of the nematic ordering field in such basic unit of porous networks is controlled by nematic orientation profiles in individual pores, anchoring frustration along the edges of joining pores and coupling to the material flow field. We numerically investigate formation of the flow-aligned configurations in single cylindrical pores and pore junctions. Depending on the arrangement of inlet and outlet flows in the junction, we demonstrate existence of numerous stationary nematic configurations, characterised by specific bulk defects and surface disclinations along joining edges. Observed bulk defects are nonsingular escaped structures, disclinations in the form of loops or disclination lines pinned to the joining edges of the pores. Furthermore, we show examples of defect dynamics during the flow-induced topological transformations.     

Computational Screening of 3 d Transition Metal Atoms Anchored on Defective Graphene for Efficient Electrocatalytic N2 Fixation

The synthesis of ammonia (NH₃) through the electrochemical reduction of molecular nitrogen (N₂) is a promising strategy for significantly reducing energy consumption compared to traditional industrial processes. Herein, we report the design of a series of monovacancy and divacancy defective graphenes decorated with single 3d transition metal atoms (TM@MVG and TM@DVG; TM=Sc−Zn) as electrocatalysts for the nitrogen-reduction reaction (NRR) aided by density functional theory (DFT) calculations. By comparing energies for N₂ adsorption as well as the free energies associated with *N₂ activation and *N₂H formation, we successfully identified V@MVG, with the lowest potential of −0.63 V, to be an effective catalytic substrate for the NRR in an enzymatic mechanism. Electronic properties, including Bader charges, charge density differences, partial densities of states, and crystal orbital Hamilton populations, are further analyzed in detail. We believe that these results help to explain recent observations in this field and provide guidance for the exploration of efficient electrocatalysts for the NRR.