Tailoring the Superatomic Characteristics and Optical Behavior of Metal-Free Boron Clusters via Ligand Engineering.

It is of great importance to understand how the number and type of ligands influence the properties of clusters through ligand engineering, as this knowledge is crucial for the rational design and optimization of functional materials. Herein, the geometrical structures, binding energies, and electronic properties of nonmetallic Bn (n = 20 and 40) clusters with CO, PEt3, F, NO2, and CN ligands are systematically explored based on density functional theory (DFT) calculations. Our findings demonstrate that the CO ligand acts as an electron donor when attached to these two boron clusters, in contrast to their role as electron acceptors in interactions with metal oxide and metal chalcogenide clusters. This emphasizes the necessity of considering the intrinsic properties of the host cluster when modifying with ligands. Moreover, it was observed that substituting PEt3 with F, NO2, or CN converted the B20 cluster from an electron acceptor to an electron donor, thereby demonstrating the versatility in tuning the redox characteristics of boron clusters by selecting appropriate ligands. Intriguingly, the attachment of the PEt3, F, NO2, and CN ligands to B20 can significantly modulate the electronic properties of B20 to realize the formation of metal-free superalkali (B20(PEt3)n, n = 3-5) and superhalogen (B20F, B20NO2, and B20CN) clusters. Furthermore, the structure, stability, and optical absorption of the charge transfer complex B20(PEt3)3+B20F were analyzed. This complex has been identified as an efficient material for harvesting visible light. Our findings provide insights into the effects of ligand variations on boron cluster functionalities, offering a new perspective for the design of advanced materials with tailored cluster properties through ligand engineering.

Regulated Surface Electronic States of CuNi Nanoparticles through Metal-Support Interaction for Enhanced Electrocatalytic CO2 Reduction to Ethanol.

Developing stable catalysts with higher selectivity and activity within a wide potential range is critical for efficiently converting CO2 to ethanol. Here, the carbon-encapsulated CuNi nanoparticles anchored on nitrogen-doped nanoporous graphene (CuNi@C/N-npG) composite are designedly prepared and display the excellent CO2 reduction performance with the higher ethanol Faradaic effiency (FEethanol  ≥ 60%) in a wide potential window (600 mV). The optimal cathodic energy efficiency (47.6%), Faradaic efficiency (84%), and selectivity (96.6%) are also obtained at -0.78 V versus reversible hydrogen electrode (RHE). Combining with the density functional theory (DFT) calculations, it is demonstrated that the stronger metal-support interaction (Ni-N-C) can regulate the surface electronic structure effectively, boosting the electron transfer and stabilizing the active sites (Cu0 -Cuδ+ ) on the surface of CuNi@C/N-npG, finally realizing the controllable transition of reaction intermediates. This work may guide the designs of electrocatalysts with highly catalytic performance for CO2 reduction to C2+ products.

Oxygen vacancy and nitrogen doping collaboratively boost performance and stability of TiO2-supported Pd catalysts for CO2 photoreduction: a DFT study.

The regulation of interfacial charge transfer, optimization of active sites, and maintenance of stability are effective strategies for improving catalytic performance. The effect of the oxygen vacancy (VO) and nitrogen doping on these parameters for CO2 photoreduction on Pd10/TiO2(101) was studied using density functional theory calculations. The results demonstrate that introduction of the VO could trigger reversed electron transfer, making the VO and Pd atoms the active center for CO2 reduction. However, the VO is repaired by the dissociated O atom. The combined effect of the VO and N is related to the position of N. Although the substitutional N (NS) can delocalize electrons at the VO, it cannot improve the activity and stability. The interstitial N (Ni) located below the VO forms Ni-Ti bonds with two Ti atoms adjacent to the VO. This can delocalize the electrons near the VO, and the five-fold-coordinated titanium (Ti5C) replaces the VO as the active center, thus enhancing the reactivity and protecting the VO. Further research indicates that the co-modification of the VO and Ni improves photoexcited electron transfer and distribution, which would in turn promote CO2 reduction. The results of this study propose that surface defect engineering holds great promise for boosting CO2 photoreduction by integrating functions of electron density modulation and catalysis.

Zn2GeO4-x/ZnS heterojunctions fabricated via in situ etching sulfurization for Pt-free photocatalytic hydrogen evolution: interface roughness and defect engineering.

Interface engineering has been regarded as a promising strategy for enhancing the catalytic activities of heterojunction photocatalysts. Herein, we have adopted an in situ etching sulfurization method to construct a Zn2GeO4-x/ZnS intimate heterojunction, which exhibited excellent photocatalytic H2 production in the absence of a Pt co-catalyst. Distinctively, TEM and HRTEM measurements showed that the interface of the Zn2GeO4-x/ZnS heterojunction became rough (topologically) due to in situ etching sulfurization, and etching was found to be strongly dependent on the crystal orientation. Moreover, the surface of the Zn2GeO4 nanorods from flat (100) planes evolved into an irregular coastline-like structure topologized with (110) and (113) high-index planes. ICP and elemental distribution measurements indicated that during the precipitation of ZnS via in situ etching sulfurization, the migration and dissolution of Zn and Ge ions on the Zn2GeO4(100) plane led to the roughening of the interface and the evolution of crystal planes. XPS and EPR analyses showed that Zn2GeO4-x/ZnS contained more oxygen vacancies with structural evolution. The theoretical calculations demonstrated that oxygen defects were prone to be generated on the Zn2GeO4(113) plane and formed the Ge3c3+-VO complexes. Compared to the inactive (100) plane, etching caused the Zn2GeO4(110) planes to have a higher number of threefold coordinated germanium (Ge3c4+) and (113) high-index planes that possessed abundant active sites (Ge3c3+-VO complexes), which dramatically decreased the barrier and reaction energy of H2O dissociation. This work not only provides fundamental insights into the topological interface evolution and facet-dependent defect distribution but also offers a strategy for the design of efficient photocatalysts for H2 production without the use of Pt as a co-catalyst based on a multifunctional interface.

Critical Role of Water and Oxygen Defects in C-O Scission during CO2 Reduction on Zn2GeO4(010).

Exploration of catalyst structure and environmental sensitivity for C-O bond scission is essential for improving the conversion efficiency because of the inertness of CO2. We performed density functional theory calculations to understand the influence of the properties of adsorbed water and the reciprocal action with oxygen vacancy on the CO2 dissociation mechanism on Zn2GeO4(010). When a perfect surface was hydrated, the introduction of H2O was predicted to promote the scission step by two modes based on its appearance, with the greatest enhancement from dissociative adsorbed H2O. The dissociative H2O lowers the barrier and reaction energy of CO2 dissociation through hydrogen bonding to preactivate the C-O bond and assisted scission via a COOH intermediate. The perfect surface with bidentate-binding H2O was energetically more favorable for CO2 dissociation than the surface with monodentate-binding H2O. Direct dissociation was energetically favored by the former, whereas monodentate H2O facilitated the H-assisted pathway. The defective surface exhibited a higher reactivity for CO2 decomposition than the perfect surface because the generation of oxygen vacancies could disperse the product location. When the defective surface was hydrated, the reciprocal action for vacancy and surface H2O on CO2 dissociation was related to the vacancy type. The presence of H2O substantially decreased the reaction energy for the direct dissociation of CO2 on O2c1- and O3c2-defect surfaces, which converts the endoergic reaction to an exoergic reaction. However, the increased decomposition barrier made the step kinetically unfavorable and reduced the reaction rate. When H2O was present on the O2c2-defect surface, both the barrier and reaction energy for direct dissociation were invariable. This result indicated that the introduction of H2O had little effect on the kinetics and thermodynamics. Moreover, the H-assisted pathway was suppressed on all hydrated defect surfaces. These results provide a theoretical perspective for the design of highly efficient catalysts.

A theoretical study of O2 activation by the Au7-cluster on Mg(OH)2: roles of surface hydroxyls and hydroxyl defects.

Using density functional theory (DFT) calculations, we investigated O2 activation by the Au7-cluster supported on the perfect and hydroxyl defective Mg(OH)2(0001) surface. It is revealed that hydroxyl groups on the perfect Mg(OH)2(0001) surface can not only enhance the stability of the Au7-cluster, but also help the adsorption of the O2 molecule through hydrogen-bonding interactions with the 2nd-layered interfacial Au sites. Density of states (DOS) analysis shows that the d-band centers of the 2nd-layered interfacial Au atoms are very close to the Fermi level, which thereby reduce the Pauli repulsion and promote the O2 adsorption. These two responses make the 2nd-layered interfacial Au atoms favor O2 activation. Interestingly, the surface hydrogen atoms activated by the 1st-layered Au atoms can facilitate the O2 dissociation process as well. Such a process is dynamically favorable and more inclined to occur at low temperatures compared to the direct dissociation process. Meanwhile, the hydroxyl defects of Mg(OH)2(0001) located right under the Au7-cluster can also up-shift the d-band centers of the surrounding Au atoms toward the Fermi level, enhancing its catalytic activity for O2 dissociation. In contrast, the d-band center of Au atoms surrounding the hydroxyl defect near the Au7-cluster exhibits an effective down-shift to lower energies, and therefore holds low activity. These results unveiled the roles of surface hydroxyls and hydroxyl defects on the Au/Mg(OH)2 catalyst in O2 activation and could provide a theoretical guidance for chemists to efficiently synthesize Au/hydroxide catalysts.

The roles of surface structure, oxygen defects, and hydration in the adsorption of CO(2) on low-index ZnGa(2)O(4) surfaces: a first-principles investigation.

The effects of the surface atomic and electronic structures, oxygen defects, and hydration on CO2 adsorption on ZnGa2O4(100), (110), and (111) surfaces were studied using density functional theory (DFT) slab calculations. For the perfect (100) surface, the most stable adsorption state involved the Zn-O-Ga bridge site, with an adsorption energy of 0.16 eV. In the case of the (110) and (111) surfaces, the strongest binding occurred on the Zn-O bridge sites, with much lower adsorption energies of -0.22 eV and -0.35 eV, respectively. In addition, the perfect surfaces showed CO2 activation ability, but dissociation adsorption could not proceed. The oxygen vacancies on these three surfaces (1) made the metal sites beside them carry less positive charge and further reduced the adsorption energies on these metal sites, and (2) created efficient adsorption sites that allowed even dissociative adsorption. The most favorable molecular and dissociative adsorption states both involved the O3c vacancy site of the (100) surface, and these two processes were spontaneous with adsorption energies of 0.74 eV and 0.80 eV, respectively. When H2O molecules are present on the perfect and defective surfaces, the generation of hydrogen bonds between H2O and CO2 would slightly enhance the stability of adsorption (except for that on the surface), making them energetically favorable. However, the co-adsorption of H2O could also increase the energy barriers for the decomposition reactions on the defective surfaces, making them kinetically unfavorable. Furthermore, the oxygen vacancy defects showed good activity for H2O adsorption and decomposition, as well. Thus, when both H2O and CO2 were present in the adsorption system, H2O would compete with CO2 for the oxygen vacancy sites and further decrease the amount of CO2 adsorption and decomposition. These findings have important implications for the decomposition of CO2 on the ZnGa2O4 surfaces and can provide theoretical guidance for chemists to efficiently synthesize ZnGa2O4 catalysts.

Pressure-induced ferroelastic phase transition in SnO2 from density functional theory.

High-pressure ferroelastic transition of rutile- to CaCl2-type SnO2 is investigated within density functional theory and Landau free energy theory. The calculated Landau energy map around the ground state is successfully used to clarify the softening mechanism of B1g mode (order parameter Q) and the coupling mechanism between the soft B1g mode and the soft transverse acoustic (TA) mode (strain ɛ). It is found that the Sn-O-Sn bending induced soft B1g mode effectively slows the excess energy increase caused by bond stretching, while the coupling between the soft B1g mode and the soft TA mode further decreases the energy since the lattice distortion strain ɛ minimizes the SnO6 octahedral distortion. Q induced Landau Gibbs free energy is interpreted as the sum of the bond stretching energy, bending energy, and octahedral distortion energy, while that induced by ɛ is interpreted as the lattice distortion energy.

Adjusted Preferential Adsorption of Intermediates via Regulation of the Electronic Structure during the Electrocatalytic CO2 Reduction Process.

The surface electronic structures of catalysts play a crucial role in CO2 adsorption and activation. Here, sulfur vacancies are introduced into CuInS2 nanosheets (Vs-CuInS2) to evaluate the effect of electronic structures at the surface-active sites on the electrochemical CO2 reduction reaction (CO2RR). Vs-CuInS2 exhibits a significant disparity in the highest FEformate/FECO (6.50) compared to that of CuInS2 (1.86). Specifically, the maximum current density (Jmax) of carbon products on Vs-CuInS2 is 78.78 mA cm-2, and a Faraday efficiency of carbon products (FEcarbon products) of ≥80% is achieved in 600 mV wide potential windows. In situ Raman measurements and density functional theory calculations elucidate the origin of the apparent alterations in the carbon product selectivity. The introduction of sulfur vacancies realizes the controllable regulation of the local electronic density around the metal active sites, inducing the transformation of *COOH and *OCHO from competitive adsorption on CuInS2 to specific adsorption on Vs-CuInS2. In addition, the regulation of electronic structures on Vs-CuInS2 inhibits *H adsorption. This work reveals the transfer of adsorption of CO2RR intermediates via regulation of the electronic structure, complementing the understanding of the mechanism for the enhanced CO2RR.

A theoretical study of water adsorption and decomposition on low-index spinel ZnGa2O4 surfaces: correlation between surface structure and photocatalytic properties.

Water adsorption and decomposition on stoichiometrically perfect and oxygen vacancy containing ZnGa2O4 (100), (110), and (111) surfaces were investigated through periodic density functional theory (DFT) calculations. The results demonstrated that water adsorption and decomposition are surface-structure-sensitive processes. On a stoichiometrically perfect surface, the most stable molecular adsorption that could take place involved the generation of hydrogen bonds. For dissociative adsorption, the adsorption energy of the (111) surface was more than 4 times the energies of the other two surfaces, indicating it to be the best surface for water decomposition. A detailed comparison of these three surfaces showed that the primary reason for this observation was the special electronic state of the (111) surface. When water dissociated on the (111) surface, the special Ga3c-4s and 4p hybridization states at the Fermi level had an obvious downshift to the lower energies. This large energy gain greatly promoted the dissociation of water. Because the generation of O(3c) vacancy defects on the (100) and (110) surfaces could increase the stability of the dissociative adsorption states with few changes to the energy barrier, this type of defect would make the decomposition of water molecules more favorable. However, for the (111) surface, the generation of vacancy defects could decrease the stability of the dissociative adsorption states and significantly increase their energy barriers. Therefore, the decomposition of water molecules on the oxygen vacancy defective (111) surface would be less favorable than the perfect (111) surface. These findings on the decomposition of H2O on the ZnGa2O4 surfaces can be used toward the synthesis of water-splitting catalysts.

A new thiophenyl pyrazoline fluorescent probe for Cu2+ in aqueous solution and imaging in live cell.

A new thiophenyl pyrazoline probe for Cu(2+) in aqueous solution was synthesized and characterized by IR, NMR, HRMS and X-ray analysis. The probe displays remarkably high selectivity and sensitivity for Cu(2+) with a detection limit of 1.919 × 10(-7) M in aqueous solution (EtOH:HEPES = 1:1, v/v, 0.02 M, pH = 7.2). In addition, the probe is further successfully used to image Cu(2+) in living cells and the probe possesses good reversibility.

Electrochemically stable frustrated Lewis pairs on dual-metal hydroxides for electrocatalytic CO2 reduction.

The sluggish kinetics of CO2 activation and reduction severely limit the energy conversion efficiency of electrocatalytic CO2 reduction into fuels. Here, ZnSn(OH)6 with an alternating arrangement of Zn(OH)6 and Sn(OH)6 octahedral units and SrSn(OH)6 with an alternating arrangement of SrO6 and Sn(OH)6 octahedral units were adopted to check the effects of frustrated Lewis pairs (FLPs) on electrochemical CO2 reduction. The FLPs were in situ electrochemically reconstructed on ZnSn(OH)6 by reducing the electrochemically unstable Sn-OH to Sn-oxygen vacancies (Sn-OVs) as a Lewis acid site, which are able to create strong interactions with the adjacent electrochemically stable Zn-OH, a Lewis base site. Compared to SrSn(OH)6 without FLPs, the higher formate selectivity of ZnSn(OH)6 originates from the strong ability of FLPs to capture protons and activate CO2via the electrostatic field of FLPs triggering better electron transfer and strong orbital interactions under negative potentials. Our findings may guide the design of electrocatalysts for CO2 reduction with high catalytic performances.

Synergistic effects in La/N codoped TiO2 anatase (101) surface correlated with enhanced visible-light photocatalytic activity.

The interaction between implanted La, substitutional N, and an oxygen vacancy at TiO(2) anatase (101) surface has been investigated by means of first-principles density function theory calculations to investigate the origin of enhanced visible-light photocatalytic activity of La/N-codoped anatase observed in experiments. Our calculations suggest that both the adsorptive and substitutional La-doped TiO(2) anatase (101) surfaces are probably defective configurations in experiments. The h-Cave-adsorbed La doping decreases the formation energy for the substitutional N implantation and vice versa, while the charge compensation effects do not take effect between the adsorptive La and substitutional N dopants, resulting in some partially occupied states in the band gap acting as traps of the photoexcited electrons. The Ti(5c)-substituted La doping decreases the energy required for the substitutional N implantation, and the substitutional La and N codoping promotes the formation of an oxygen vacancy, which migrates from the O(sb-3c) site at the inner layer toward the surface O(b) site. For the substitutional La/N-codoped (Ti(5c)_O(3c-down)) surface, the charge compensation between the substitutional La and substitutional N leads to the formation of two isolated occupied N(s)-O π* impurity levels in the gap, while the excitation energy from the higher impurity level to the CBM decreases by about 0.89 eV. After further considering an oxygen vacancy on the Ti(5c)_O(3c-down) surface, the two electrons on the double donor levels (O(b) vacancy) passivate the same amount of holes on the acceptor levels (substitutional La and N), forming the acceptor-donor-acceptor compensation pair, which provides a reasonable mechanism for the enhanced visible-light photocatalytic activity of La/N codoped TiO(2) anatase. This knowledge may aid the further design and construction of new effective visible-light photocatalysts.

Surface dependence of CO2 adsorption on Zn2GeO4.

An understanding of the interaction between Zn(2)GeO(4) and the CO(2) molecule is vital for developing its role in the photocatalytic reduction of CO(2). In this study, we present the structure and energetics of CO(2) adsorbed onto the stoichiometric perfectly and the oxygen vacancy defect of Zn(2)GeO(4) (010) and (001) surfaces using density functional theory slab calculations. The major finding is that the surface structure of the Zn(2)GeO(4) is important for CO(2) adsorption and activation, i.e., the interaction of CO(2) with Zn(2)GeO(4) surfaces is structure-dependent. The ability of CO(2) adsorption on (001) is higher than that of CO(2) adsorption on (010). For the (010) surface, the active sites O(2c)···Ge(3c) and Ge(3c)-O(3c) interact with the CO(2) molecule leading to a bidentate carbonate species. The presence of Ge(3c)-O(2c)···Ge(3c) bonds on the (001) surface strengthens the interaction of CO(2) with the (001) surface, and results in a bridged carbonate-like species. Furthermore, a comparison of the calculated adsorption energies of CO(2) adsorption on perfect and defective Zn(2)GeO(4) (010) and (001) surfaces shows that CO(2) has the strongest adsorption near a surface oxygen vacancy site, with an adsorption energy -1.05 to -2.17 eV, stronger than adsorption of CO(2) on perfect Zn(2)GeO(4) surfaces (E(ads) = -0.91 to -1.12 eV) or adsorption of CO(2) on a surface oxygen defect site (E(ads) = -0.24 to -0.95 eV). Additionally, for the defective Zn(2)GeO(4) surfaces, the oxygen vacancies are the active sites. CO(2) that adsorbs directly at the Vo site can be dissociated into CO and O and the Vo defect can be healed by the oxygen atom released during the dissociation process. On further analysis of the dissociative adsorption mechanism of CO(2) on the surface oxygen defect site, we concluded that dissociative adsorption of CO(2) favors the stepwise dissociation mechanism and the dissociation process can be described as CO(2) + Vo → CO(2)(δ-)/Vo → CO(adsorbed) + O(surface). This result has an important implication for understanding the photoreduction of CO(2) by using Zn(2)GeO(4) nanoribbons.

Theoretical insight into the structural stability of KZnB3O6 polymorphs with different BO(x) polyhedral networks.

In general, the presence of shared edges of polyhedra for high-valence low-coordinated small cations is rarely seen except under extreme conditions such as high pressure. However, the ambient-pressure synthesis of KZnB(3)O(6) built of edge-sharing BO(4) tetrahedra is contrary to this. By investigating the molecular dynamics, lattice dynamics, and electronic properties via density functional theory, we studied the origin of the phase stability of the edge-sharing (es) and "corner-sharing (cs)" KZnB(3)O(6). Lattice dynamics results show that there are no phonon anomalies that could lead to the instability of es-KZnB(3)O(6), which is consistent with molecular dynamics analysis. For "cs-KZnB(3)O(6)", a soft mode at the G point in the phonon dispersion is identified that reflects the dynamic instability with respect to small distortions. Eigenvector analysis of the soft mode of "cs-KZnB(3)O(6)" indicates that the instability comes from the linkage of ZnO(5) polyhedra rather than BO(x) polyhedra. Electronic property calculation indicates that the edge-sharing BO(4) polyhedra connected by the longest B-O σ bonds provide a solid framework for es-KZnB(3)O(6). In the case of "cs-KZnB(3)O(6)", the overlong Zn-O bond possesses the smallest covalent nature and the least orbital overlap among the bonds in a ZnO(5) polyhedron, and these two features of the electronic structure reduce the stability of "cs-KZnB(3)O(6)" compared to es-KZnB(3)O(6). The electronic property calculation further confirms the results obtained from lattice dynamics analysis.

Highly Effective Photocatalytic Radical Reactions Triggered by a Photoactive Metal-Organic Framework.

On account of their inherent reactive properties, radical reactions play an important role in organic syntheses. The booming photochemistry provides a feasible approach to trigger the generation of radical intermediates in organic reaction processes. Thus, developing effective photocatalysts becomes the key step in radical reactions. In this work, the triphenylamine moiety with photoactivity is successfully embedded in a highly porous and stable metal-organic framework (MOF), and the obtained MOF, namely, Zr-TCA, naturally displays a photoactive property derived from the triphenylamine-based ligand. In photocatalytic studies, the triphenylamine-based Zr-TCA not only exhibits a high catalytic activity on the aerobic oxidation of sulfides via the generation of the superoxide radical anion (O2•-) under light irradiation but also shows good efficiency in the trifluoromethylation of arenes and heteroarenes by the formation of the trifluoromethyl radical (CF3•) as an intermediate. Moreover, the high performance of Zr-TCA can be well maintained over a wide range of substrates in these radical reactions, and the recycled Zr-TCA still retains its excellent photocatalytic activity. The high recyclability and catalytic efficiency to various substrates make the constructed triphenylamine-based Zr-TCA a promising photocatalyst in diverse radical reactions.

Origin of improved visible photocatalytic activity of nitrogen/hydrogen codoped cubic In2O3: first-principles calculations.

We have employed DFT calculations to carry out an accurate analysis of the effect of N- and NH-doping on the visible photocatalytic activity in the cubic In(2)O(3). In the substitutional N-doped In(2)O(3), the 2p impurity states of N induce a red shift in the optical absorption, while in the interstitial N-doping the red shift is dominantly caused by the localized π antibonding states of NO. When a H atom is accompanied by a N impurity in the lattice, the H atom acts as a charge donor and compensates the hole state created by N-doping, thus the energy level of the impurity states is reduced. As a result, the mixing of impurity states and the valence band is enhanced. At the same nitrogen dopant concentration, NH-codoping yields a larger band gap narrowing, especially for the interstitial NH-codoping. The theoretical calculations presented in this work explain well the previous experimental results of the enhanced visible photocatalytic activity in NH-codoped cubic In(2)O(3).

First-principles study of the electronic, optical properties and lattice dynamics of tantalum oxynitride.

First-principles calculations of the electronic, optical properties and lattice dynamics of tantalum oxynitride are performed with the density functional theory plane-wave pseudopotential method. The analysis of the electronic structure shows a covalent nature in Ta-N bonds and Ta-O bonds. The hybridization of anion 2p and Ta 5d states results in enhanced dispersion of the valence band, raising the top of the valence band and leading to the visible-light response in TaON. It has a high dielectric constant, and the anisotropy is displayed obviously in the lower energy region. Our calculation indicated that TaON has excellent dielectric properties along [010] direction. Various optical properties, including the reflectivity, absorption coefficient, refractive index, and the energy-loss spectrum are derived from the complex dielectric function. We also present phonon dispersion relation, zone-center optical mode frequency, density of phonon states, and some thermodynamic properties. The experimental IR modes (B(u) at 808 cm(-1) and A(u) at 863 cm(-1)) are reproduced well and assigned to a combination of stretching and bending vibrations for the Ta-N bond and Ta-O bond. The thermodynamic properties of TaON, such as heat capacity and Debye temperature, which were important parameters for the measurement of crystal physical properties, were first given for reference. Our investigations provide useful information for the potential application of this material.

Optical properties of the high-pressure phases of SnO(2): first-principles calculation.

We present a detailed investigation on the optical properties, including dielectric function, reflectivity, absorption, refractive index, and electron energy-loss spectrum, of the high-pressure phase SnO(2) in the rutile, pyrite, fluorite, and cotunnite structures by using the density functional theory (DFT) plane-wave pseudopotential method. The results indicate that with the increasing of pressure the band gaps become larger, the density of states are broader, so the curves of optical properties have a little blue shift. Except that the fluorite phase has some metallic properties, the other three phases exhibit excellent dielectric behavior. Interestingly, the fluorite and cotunnite SnO(2) phases always have some special characteristics, such as higher plasma frequency, which need further fundamental and application research.

Amorphous TiO2 as a multifunctional interlayer for boosting the efficiency and stability of the CdS/cobaloxime hybrid system for photocatalytic hydrogen production.

The construction of both highly efficient and stable hybrid artificial photosynthetic systems comprising semiconductors as photosensitizers and abundant metal-based molecular complexes as cocatalysts for photocatalytic H2 generation remains challenging. Herein, we report an effective and stable CdS/cobaloxime hybrid system prepared by inserting an amorphous TiO2 (a-TiO2) interlayer with adjustable thickness and by covalently-surface-attaching molecular cobaloxime catalysts. This hybrid system displayed outstanding photocatalytic H2 production and reached a maximum rate of ∼25 mmol g-1 h-1, which was ∼20.8 times that of pure CdS and 1.7 times that of the CdS/cobaloxime system without an a-TiO2 interlayer (CdS/Co). More importantly, 6 nm a-TiO2 uniformly coated CdS nanorods (CdS NRs) exhibited exceptional 200 h long-term catalytic behaviour under ≥420 nm visible light irradiation. However, the H2 production performance of the CdS/Co hybrid system decreased significantly over 10 h. Density functional theory (DFT) calculations indicated that the a-TiO2 surface can provide abundant bonding sites for the effective immobilization of molecular catalysts. Moreover, Mott-Schottky electrochemical measurements and femtosecond transient absorption spectroscopy revealed that the a-TiO2 interlayer had favourable band levels that could fasten the photoexcited electron transfer from CdS to molecular cobaloxime and could extract holes with intraband electronic states generated by defects, thus prohibiting CdS photocorrosion and improving the stability of the hybrid system. This study proposes a strategy for designing multifunctional interlayers for the effective immobilization of molecular catalysts, beneficial regulation of photoinduced charge carriers, and improvement of the stability as well as facilitation of the construction of artificial photosynthetic hybrid systems with high efficiency and durability.