Combined Analyses on Electronic Structure and Molecular Orbitals of d10 Bimetal Oxide In2Ge2O7 and Photocatalytic Performances for Overall Water Splitting and CO2 Reduction.

Semiconducting photocatalytic overall water splitting and CO2 reduction are possible solutions to the emerging worldwide challenges of oil shortage and continual temperature increase, and the key is to develop an efficient photocatalyst. Most photocatalysts contain the d0, d10 or d10ns2 metals, and a guiding principle is desired to help to distinguish outstanding semiconductors. Here, the d10 bimetal oxide In2Ge2O7 was selected as the target. First, density functional theory (DFT) calculations point out that the nonbonding O 2p orbitals dominate the valence band maximum (VBM), and In 5s-O 2s and Ge 4s-O 2s antibonding orbitals are the major components of conduction band minimum (CBM). Moreover, the molecular orbitals were analyzed to consolidate the DFT calculations and make it more understandable for chemists. Due to the very small specific surface area (0.51 m2/g) and wide band gap (4.14 eV), as-prepared In2Ge2O7 did not exhibit any overall water splitting activity; nevertheless, when loading with 1 wt% cocatalyst (i.e., Pt, Pd), the surficial charge recombination can be greatly eliminated and the overall water splitting activity is significantly improved to 33.0(4) and 17.2(7) µmol/h for H2 and O2 generation, respectively. The apparent quantum yield (AQY) at 254 nm is 8.28%. This observation is proof that the inherent electronic structure of In2Ge2O7 is beneficial for the charge migration in bulk. Moreover, this catalyst also exhibits an observable CO2 reduction activity in pure water, which is a competition reaction with water splitting, anyway, the CH4 selectivity can be enhanced by loading Pd. This is a successful attempt to unravel the structure-property relationship by combining the analyses on electronic structure and molecular orbitals and is enlightening to further discover good candidates to photocatalysts.

Understanding ion-induced assembly of cellulose nanofibrillar gels through shear-free mixing and in situ scanning-SAXS.

During the past decade, cellulose nanofibrils (CNFs) have shown tremendous potential as a building block to fabricate new advanced materials that are both biocompatible and biodegradable. The excellent mechanical properties of the individual CNF can be transferred to macroscale fibers through careful control in hydrodynamic alignment and assembly processes. The optimization of such processes relies on the understanding of nanofibril dynamics during the process, which in turn requires in situ characterization. Here, we use a shear-free mixing experiment combined with scanning small-angle X-ray scattering (scanning-SAXS) to provide time-resolved nanoscale kinetics during the in situ assembly of dispersed cellulose nanofibrils (CNFs) upon mixing with a sodium chloride solution. The addition of monovalent ions led to the transition to a volume-spanning arrested (gel) state. The transition of CNFs is associated with segmental aggregation of the particles, leading to a connected network and reduced Brownian motion, whereby an aligned structure can be preserved. Furthermore, we find that the extensional flow seems to enhance the formation of these segmental aggregates, which in turn provides a comprehensible explanation for the superior material properties obtained in shear-free processes used for spinning filaments from CNFs. This observation clearly highlights the need for different assembly strategies depending on morphology and interactions of the dispersed nanoparticles, where this work can be used as a guide for improved nanomaterial processes.

Shear-free mixing to achieve accurate temporospatial nanoscale kinetics through scanning-SAXS: ion-induced phase transition of dispersed cellulose nanocrystals.

Time-resolved in situ characterization of well-defined mixing processes using small-angle X-ray scattering (SAXS) is usually challenging, especially if the process involves changes of material viscoelasticity. In specific, it can be difficult to create a continuous mixing experiment without shearing the material of interest; a desirable situation since shear flow both affects nanoscale structures and flow stability as well as resulting in unreliable time-resolved data. Here, we demonstrate a flow-focusing mixing device for in situ nanostructural characterization using scanning-SAXS. Given the interfacial tension and viscosity ratio between core and sheath fluids, the core material confined by sheath flows is completely detached from the walls and forms a zero-shear plug flow at the channel center, allowing for a trivial conversion of spatial coordinates to mixing times. With this technique, the time-resolved gel formation of dispersed cellulose nanocrystals (CNCs) was studied by mixing with a sodium chloride solution. It is observed how locally ordered regions, so called tactoids, are disrupted when the added monovalent ions affect the electrostatic interactions, which in turn leads to a loss of CNC alignment through enhanced rotary diffusion. The demonstrated flow-focusing scanning-SAXS technique can be used to unveil important kinetics during structural formation of nanocellulosic materials. However, the same technique is also applicable in many soft matter systems to provide new insights into the nanoscale dynamics during mixing.

Cross-Sections of Nanocellulose from Wood Analyzed by Quantized Polydispersity of Elementary Microfibrils.

Bio-based nanocellulose has been shown to possess impressive mechanical properties and simplicity for chemical modifications. The chemical properties are largely influenced by the surface area and functionality of the nanoscale materials. However, finding the typical cross-sections of nanocellulose, such as cellulose nanofibers (CNFs), has been a long-standing puzzle, where subtle changes in extraction methods seem to yield different shapes and dimensions. Here, we extracted CNFs from wood with two different oxidation methods and variations in degree of oxidation and high-pressure homogenization. The cross-sections of CNFs were characterized by small-angle X-ray scattering and wide-angle X-ray diffraction in dispersed and freeze-dried states, respectively, where the results were analyzed by assuming that the cross-sectional distribution was quantized with an 18-chain elementary microfibril, the building block of the cell wall. We find that the results agree well with a pseudosquare unit having a size of about 2.4 nm regardless of sample, while the aggregate level strongly depends on the extraction conditions. Furthermore, we find that aggregates have a preferred cohesion of phase boundaries parallel to the (110)-plane of the cellulose fibril, leading to a ribbon shape on average.

Cellulose nanofibrils and nanocrystals in confined flow: Single-particle dynamics to collective alignment revealed through scanning small-angle x-ray scattering and numerical simulations.

Nanostructured materials made through flow-assisted assembly of proteinaceous or polymeric nanosized fibrillar building blocks are promising contenders for a family of high-performance biocompatible materials in a wide variety of applications. Optimization of these processes relies on improving our knowledge of the physical mechanisms from nano- to macroscale and especially understanding the alignment of elongated nanoparticles in flows. Here, we study the full projected orientation distributions of cellulose nanocrystals (CNCs) and nanofibrils (CNFs) in confined flow using scanning microbeam SAXS. For CNCs, we further compare with a simulated system of dilute Brownian ellipsoids, which agrees well at dilute concentrations. However, increasing CNC concentration to a semidilute regime results in locally arranged domains called tactoids, which aid in aligning the CNC at low shear rates, but limit alignment at higher rates. Similarly, shear alignment of CNF at semidilute conditions is also limited owing to probable bundle or flock formation of the highly entangled nanofibrils. This work provides a quantitative comparison of full projected orientation distributions of elongated nanoparticles in confined flow and provides an important stepping stone towards predicting and controlling processes to create nanostructured materials on an industrial scale.

Reinforcement of Natural Rubber Latex Using Jute Carboxycellulose Nanofibers Extracted Using Nitro-Oxidation Method.

Synthetic rubber produced from nonrenewable fossil fuel requires high energy costs and is dependent on the presumed unstable petroleum price. Natural rubber latex (NRL) is one of the major alternative sustainable rubber sources since it is derived from the plant 'Hevea brasiliensis'. Our study focuses on integrating sustainably processed carboxycellulose nanofibers from untreated jute biomass into NRL to enhance the mechanical strength of the material for various applications. The carboxycellulose nanofibers (NOCNF) having carboxyl content of 0.94 mmol/g was prepared and integrated into its nonionic form (-COONa) for its higher dispersion in water to increase the interfacial interaction between NRL and NOCNF. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) analyses of NOCNF showed the average dimensions of nanofibers were length (L) = 524 ± 203 nm, diameter (D) 7 ± 2 nm and thickness 2.9 nm. Furthermore, fourier transform infra-red spectrometry (FTIR) analysis of NOCNF depicted the presence of carboxyl group. However, the dynamic light scattering (DLS) measurement of NRL demonstrated an effective diameter in the range of 643 nm with polydispersity of 0.005. Tensile mechanical strengths were tested to observe the enhancement effects at various concentrations of NOCNF in the NRL. Mechanical properties of NRL/NOCNF films were determined by tensile testing, where the results showed an increasing trend of enhancement. With the increasing NOCNF concentration, the film modulus was found to increase quite substantially, but the elongation-to-break ratio decreased drastically. The presence of NOCNF changed the NRL film from elastic to brittle. However, at the NOCNF overlap concentration (0.2 wt. %), the film modulus seemed to be the highest.

Facile synthesis of TiO2/CNC nanocomposites for enhanced Cr(VI) photoreduction: Synergistic roles of cellulose nanocrystals.

In this study, TiO2 nanocrystals were synthesized in the scaffold of cellulose nanocrystal (CNC) using in situ hydrolysis, where the morphology and size of TiO2 was controlled by CNC's functional groups and surface charge. The resulting TiO2/CNC nanocomposites showed a superior photocatalytic activity for Cr(VI) reduction under visible light (λ > 420 nm) due to the combined effects of small TiO2 size and ligand-to-metal charge transfer (LMCT) complex between CNC and TiO2. It was found that the charge-enriched CNC not only acted as a template to direct the crystal growth of TiO2, but also played essential roles on light harvesting and charge transfer thereby promoting the photoreduction of Cr(VI). The demonstrated system represents a unique pathway to develop a lower cost and efficient purification material for remediation of Cr(VI).

A study of TiO2 nanocrystal growth and environmental remediation capability of TiO2/CNC nanocomposites.

Nanocellulose, which can be derived from any cellulosic biomass, has emerged as an appealing nanoscale scaffold to develop inorganic-organic nanocomposites for a wide range of applications. In this study, titanium dioxide (TiO2) nanocrystals were synthesized in the cellulose nanocrystal (CNC) scaffold using a simple approach, i.e., hydrolysis of a titanium oxysulfate precursor in a CNC suspension at low temperature. The resulting TiO2 nanoparticles exhibited a narrow size range between 3 and 5 nm, uniformly distributed on and strongly adhered to the CNC surface. The structure of the resulting nanocomposite was evaluated by transmission electron microscopy (TEM) and X-ray diffraction (XRD) methods. The growth mechanism of TiO2 nanocrystals in the CNC scaffold was also investigated by solution small-angle X-ray scattering (SAXS), where the results suggested the mineralization process could be described by the Lifshitz-Slyozov-Wagner theory for Ostwald ripening. The demonstrated TiO2/CNC nanocomposite system exhibited excellent performance in dye degradation and antibacterial activity, suitable for a wide range of environmental remediation applications.

Characterization of Nanocellulose Using Small-Angle Neutron, X-ray, and Dynamic Light Scattering Techniques.

Nanocellulose extracted from wood pulps using TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidation and sulfuric acid hydrolysis methods was characterized by small-angle neutron scattering (SANS), small-angle X-ray scattering (SAXS), and dynamic light scattering (DLS) techniques. The dimensions of this nanocellulose (TEMPO-oxidized cellulose nanofiber (TOCN) and sulfuric acid hydrolyzed cellulose nanocrystal (SACN)) revealed by the different scattering methods were compared with those characterized by transmission electron microscopy (TEM). The SANS and SAXS data were analyzed using a parallelepiped-based form factor. The width and thickness of the nanocellulose cross section were ∼8 and ∼2 nm for TOCN and ∼20 and ∼3 nm for SACN, respectively, where the fitting results from SANS and SAXS profiles were consistent with each other. DLS was carried out under both the VV mode with the polarizer and analyzer parallel to each other and the HV mode having them perpendicular to each other. Using rotational and translational diffusion coefficients obtained under the HV mode yielded a nanocellulose length qualitatively consistent with that observed by TEM, whereas the length derived by the translational diffusion coefficient under the VV mode appeared to be overestimated.

Access to a new class of synthetic building blocks via trifluoromethoxylation of pyridines and pyrimidines.

Since the first synthesis of trifluoromethyl ethers in 1935, the trifluoromethoxy (OCF3) group has made a remarkable impact in medicinal, agrochemical, and materials science research. However, our inability to facilely incorporate the OCF3 group into molecules, especially heteroaromatics, has limited its potential across a broad spectrum of technological applications. Herein, we report a scalable and operationally simple protocol for regioselective trifluoromethoxylation of a wide range of functionalized pyridines and pyrimidines under mild reaction conditions. The trifluoromethoxylated products are useful scaffolds that can be further elaborated by amidation and palladium-catalysed cross coupling reactions. Mechanistic studies suggest that a radical O-trifluoromethylation followed by the OCF3-migration reaction pathway is operable. Given the unique properties of the OCF3 group and the ubiquity of pyridine and pyrimidine in biologically active molecules and functional materials, trifluoromethoxylated pyridines and pyrimidines could serve as valuable building blocks for the discovery and development of new drugs, agrochemicals, and materials.

Trifluoromethoxylation of arenes: synthesis of ortho-trifluoromethoxylated aniline derivatives by OCF3 migration.

Aryl trifluoromethoxylation by a two-step sequence of O-trifluoromethylation of N-aryl-N-hydroxylamine derivatives and intramolecular OCF3  migration is presented. This protocol allows easy access to a wide range of synthetically useful ortho-OCF3 aniline derivatives. In addition, it utilizes bench-stable reagents, is operationally simple, shows high functional-group tolerance, and is amenable to gram-scale as well as one-pot synthesis. A reaction mechanism of a heterolytic cleavage of the NOCF3 bond followed by recombination of the resulting nitrenium ion and trifluoromethoxide is proposed for the OCF3 -migration reaction.

A CO2- and temperature-switchable "schizophrenic" block copolymer: from vesicles to micelles.

CO2-responsiveness is imported into amphiphilic block copolymers, poly[(N,N-diethylaminoethyl methacrylate)-b-(N-isopropylacrylamide)] (PDEAEMA-b-PNIPAM), and a system dual-responsive to CO2 and temperature is constructed. The copolymer self-assembles in aqueous solution, and undergoes phase transition when CO2 and temperature stimuli occur, since the stimuli give rise to the conversion of the hydrophilicity of both blocks. Combining CO2 and temperature as triggers, schizophrenic micelle to vesicle morphological transition of the polymer assemblies is controlled.