Diastereo-divergent synthesis of chiral hindered ethers via a synergistic calcium(II)/gold(I) catalyzed cascade hydration/1,4-addition reaction.

Hindered ethers are ubiquitous in natural products and bioactive molecules. However, developing an efficient method for the stereocontrolled synthesis of all stereoisomers of chiral hindered ethers is highly desirable but challenging. Here we show a strategy that utilizes in situ-generated water as a nucleophile in an asymmetric cascade reaction involving two highly reactive intermediates, 3-furyl methyl cations and ortho-quinone methides (o-QMs), to synthesize chiral hindered ethers. The Ca(II)/Au(I) synergistic catalytic system enables the control of diastereoselectivity and enantioselectivity by selecting suitable chiral phosphine ligands in this cascade hydration/1,4-addition reaction, affording all four stereoisomers of a diverse range of chiral tetra-aryl substituted ethers with high diastereoselectivities (up to >20/1) and enantioselectivities (up to 95% ee). This work provides an example of chiral Ca(II)/Au(I) bimetallic catalytic system controlling two stereogenic centers via a cascade reaction in a single operation.

Development of a novel Ba2BiV3O11 photocatalyst with dual functions of both water oxidation and proton reduction performance.

To overcome the limitation of photocatalysts with dual functionality of water oxidation and proton reduction, we proposed a novel bismuth-based Ba2BiV3O11 (BBVO) photocatalyst, which can simultaneously drive the proton reduction reaction under UV light and water oxidation reaction under visible light. After doping with sulfur through an in situ vulcanization strategy, the light absorption and charge separation efficiencies of the sulfur-doped BBVO were significantly improved, thus boosting its oxygen evolution activity (64 µmol h-1) by more than 16 times compared with independent BBVO. The experimental results demonstrate that BBVO can be employed as a very promising bismuth-based photocatalyst for solar energy conversion.

Asymmetric Sites on the ZnZrOx Catalyst for Promoting Formate Formation and Transformation in CO2 Hydrogenation.

The role of formate species for CO2 hydrogenation is still under debate. Although formate has been frequently observed and commonly proposed as the possible intermediate, there is no definite evidence for the reaction of formate species for methanol production. Here, formate formation and conversion over the ZnZrOx solid solution catalyst are investigated by in situ/operando diffuse reflectance infrared Fourier transform spectroscopy-mass spectroscopy (DRIFTS-MS) coupled with density functional theory (DFT) calculations. Spectroscopic results show that bidentate carbonate formed from CO2 adsorption is hydrogenated to formate on Zn-O-Zr sites (asymmetric sites), where the Zn site is responsible for H2 activation and the Zr site is beneficial for the stabilization of reaction intermediates. The asymmetric Zn-O-Zr sites with adjacent and inequivalent features on the ZnZrOx catalyst promote not only formate formation but also its transformation. Both theoretical and experimental results demonstrate that the origin of the excellent performance of the ZnZrOx catalyst for methanol formation is associated with the H2 heterolytic cleavage promoted by the asymmetric Zn and Zr sites.

Flux-assisted synthesis of tungsten-doped layered perovskite oxychloride with promoted visible-light-responsive O2 evolution performance.

Here, we successfully prepared Ba2Bi3Ta2O11Cl via a simple one-step molten salt method and adjusted its crystal morphology and structure, based on which the O2-evolving activity was significantly improved. In addition, W doping promotes the charge separation efficiency, lowers the energy barrier for water oxidation reaction, and thus improves the activity. Finally, the optimized W-doped sample after molten salt treatment shows the best O2 production activity (55 µmol h-1) without loading any cocatalyst, which is 6 times higher than that of pristine Ba2Bi3Ta2O11Cl and 2 times higher than that of the undoped Ba2Bi3Ta2O11Cl treated with molten salt, respectively.

Suppressing non-radiative recombination in metal halide perovskite solar cells by synergistic effect of ferroelasticity.

The low fraction of non-radiative recombination established the foundation of metal halide perovskite solar cells. However, the origin of low non-radiative recombination in metal halide perovskite materials is still not well-understood. Herein, we find that the non-radiative recombination in twinning-tetragonal phase methylammonium lead halide (MAPbIxCl3-x) is apparently suppressed by applying an electric field, which leads to a remarkable increase of the open-circuit voltage from 1.12 V to 1.26 V. Possible effects of ionic migration and light soaking on the open-circuit voltage enhancement are excluded experimentally by control experiments. Microscopic and macroscopic characterizations reveal an excellent correlation between the ferroelastic lattice deformation and the suppression of non-radiative recombination. The calculation result suggests the existence of lattice polarization in self-stabilizable deformed domain walls, indicating the charge separation that facilitated by lattice polarization is accountable for the suppressed non-radiative recombination. This work provides an understanding of the excellent performance of metal halide perovskite solar cells.

Layered ß-ZrNBr Nitro-Halide as Multifunctional Photocatalyst for Water Splitting and CO2 Reduction.

Developing mixed-anion semiconductors for solar fuel production has inspired extensive interest, but the nitrohalide-based photocatalyst is still in shortage. Here we report a layered nitro-halide ß-ZrNBr with a narrow band gap of ca. 2.3 eV and low defect density to exhibit multifunctionalities for photocatalytic water reduction, water oxidation and CO2 reduction under visible-light irradiation. As confirmed by the results of electron paramagnetic resonance (EPR) and density functional theory (DFT) calculations, the formation of anion vacancies in the nitro-halide photocatalyst was inhibited due to its relatively high formation energy. Furthermore, performance of ß-ZrNBr can be effectively promoted by a simple exfoliation into nanosheets to shorten the carrier transfer distance as well as to promote charge separation. Our work extends the territory of functional photocatalysts into the nitro-halide, which opens a new avenue for fabricating efficient artificial photosynthesis.

Switching between classical/nonclassical crystallization pathways of TS-1 zeolite: implication on titanium distribution and catalysis.

In the MFI zeolite crystallization process, the classical crystallization mechanism based upon the addition of silica species is often concomitant with the nonclassical route that is characteristic of the attachment of silica nanoparticle precursors. However, the factors that govern the preferences for each mechanism remain unclear. In this work, we present the impact of switching between these two crystallization pathways on the active sites and the resulting catalytic performance of the titanosilicate TS-1 zeolite. By controlling the self-assembled precursor structures in the early crystallization stage which are mediated by the Ti and H2O in the reaction system, we could achieve the preferred modes of crystal growth of the TS-1 zeolite. We indicate that by directing the predominant crystallization path from the classical to the nonclassical route, it is possible to generate more stable bridging peroxo species upon reaction with hydrogen peroxide, as confirmed by 17O solid-state nuclear magnetic resonance spectroscopy, thus substantially increasing the catalytic performance of the resulting TS-1 for olefin epoxidation.

Pyrochlore-structural Nd2Ta2O5N2 photocatalyst with an absorption edge of over 600 nm for Z-scheme overall water splitting.

A pyrochlore-structural oxynitride Nd2Ta2O5N2 with a visible light absorption edge of ca. 620 nm was explored for photocatalytic water splitting. Dual functions of Nd2Ta2O5N2 were confirmed by proton reduction and water oxidation half-reactions through separately loading Pt or CoOx as a cocatalyst in the presence of the corresponding sacrificial reagent. Finally, the platinum modified sample (Pt/Nd2Ta2O5N2) was prepared and employed as the H2-evolving photocatalyst to fabricate an effective photocatalytic Z-scheme overall water splitting together with PtOx/WO3 as the O2-evolving photocatalyst and IO3-/I- as shuttle ions under visible light irradiation.

Water-Stable Nickel Metal-Organic Framework Nanobelts for Cocatalyst-Free Photocatalytic Water Splitting to Produce Hydrogen.

Development of water-stable metal-organic frameworks (MOFs) for promising visible-light-driven photocatalytic water splitting is highly desirable but still challenging. Here we report a novel p-type nickel-based MOF single crystal (Ni-TBAPy-SC) and its exfoliated nanobelts (Ni-TBAPy-NB) that can bear a wide range of pH environment in aqueous solution. Both experimental and theoretical results indicate a feasible electron transfer from the H4TBAPy ligand (light-harvesting center) to the Ni-O cluster node (catalytic center), on which water splitting to produce hydrogen can be efficiently driven free of cocatalyst. Compared to the single crystal, the exfoliated two-dimensional (2D) nanobelts show more efficient charge separation due to its shortened charge transfer distance and remarkably enhanced active surface areas, resulting in 164 times of promoted water reduction activity. The optimal H2 evolution rate on the nanobelt reaches 98 µmol h-1 (ca. 5 mmol h-1 g-1) showing benchmarked apparent quantum efficiency (AQE) of 8.0% at 420 nm among water-stable MOFs photocatalysts.

Catalytic production of low-carbon footprint sustainable natural gas.

Natural gas is one of the foremost basic energy sources on earth. Although biological process appears as promising valorization routes to transfer biomass to sustainable methane, the recalcitrance of lignocellulosic biomass is the major limitation for the production of mixing gas to meet the natural gas composition of pipeline transportation. Here we develop a catalytic-drive approach to directly transfer solid biomass to bio-natural gas which can be suitable for the current infrastructure. A catalyst with Ni2Al3 alloy phase enables nearly complete conversion of various agricultural and forestry residues, the total carbon yield of gas products reaches up to 93% after several hours at relative low-temperature (300 degrees Celsius). And the catalyst shows powerful processing capability for the production of natural gas during thirty cycles. A low-carbon footprint is estimated by a preliminary life cycle assessment, especially for the low hydrogen pressure and non-fossil hydrogen, and technical economic analysis predicts that this process is an economically competitive production process.

Mechanistic Studies on Photocatalytic Overall Water Splitting over Ga2O3-Based Photocatalysts by Operando MS-FTIR Spectroscopy.

Photocatalytic water splitting on semiconductor photocatalysts is one of the most important physichemical processes, but its surface reaction mechanisms are not fully understood. Based upon the ATR-FTIR investigations combining with the mass spectroscopy (MS) analysis, a direct hydroxyl radical formation mechanism that is different from those observed for other semiconductor photocatalysts is proposed. This study provides the insight into overall water splitting mechanism on Ga2O3-based photocatalysts at a molecular level, and it helps one to further understand the photocatalysis on semiconductor photocatalysts.

Synthesis of Aluminophosphate Molecular Sieves in Alkaline Media.

Unlike conventional aluminosilicate zeolites synthesized in alkaline media, aluminophosphate molecular sieves (AlPOs) have always been prepared under acidic conditions in the past three decades; this has been regarded as one of essential factors for synthesis, except for the case of silica-substituted analogues (SAPOs). For the first time, we demonstrate herein a simple and generalized route for synthesizing various types of aluminophosphate molecular sieves in alkaline media. A series of aluminophosphate sieves and their analogues have been prepared with different quaternary ammonium cations as structure-directing agents in this manner. The above successes have extended the systematic media from acidic or neutral to alkaline for the preparation of a series of aluminophosphate molecular sieves, which possibly open an alternative route for the synthesis of aluminophosphate molecular sieves.

Titanosilicate zeolite precursors for highly efficient oxidation reactions.

Titanosilicate zeolites are catalysts of interest in the field of fine chemicals. However, the generation and accessibility of active sites in titanosilicate materials for catalyzing reactions with large molecules is still a challenge. Herein, we prepared titanosilicate zeolite precursors with open zeolitic structures, tunable pore sizes, and controllable Si/Ti ratios through a hydrothermal crystallization strategy by using quaternary ammonium templates. A series of quaternary ammonium ions are discovered as effective organic templates. The prepared amorphous titanosilicate zeolites with some zeolite framework structural order have extra-large micropores and abundant octahedrally coordinated isolated Ti species, which lead to a superior catalytic performance in the oxidative desulfurization of dibenzothiophene (DBT) and epoxidation of cyclohexene. It is anticipated that the amorphous prezeolitic titanosilicates will benefit the catalytic conversion of bulky molecules in a wide range of reaction processes.

Sustainable Synthesis of Pure Silica Zeolites from a Combined Strategy of Zeolite Seeding and Alcohol Filling.

Currently, the synthesis of pure silica zeolites always requires the presence of organic structure-directing agents (OSDAs), which direct the assembly pathway and ultimately fill the pore space. A sustainable route is now reported for synthesizing pure silica zeolites in the absence of OSDAs from a combined strategy of zeolite seeding and alcohol filling, where the zeolite seeds direct crystallization of zeolite crystals from amorphous silica, while the alcohol is served as pore filling in the zeolites. Very importantly, the alcohol could be fully washed out from zeolite pores by water at room temperature, which completely avoids calcination at high temperature for removal of OSDAs in the synthesis of pure silica zeolites.

Stereostructural Elucidation of Glucose Phosphorylation by Raman Optical Activity.

Phosphorylation of glucose is the prime step in sugar metabolism and energy storage. Two key glucose phosphates are involved, that is, glucose 6-phosphate (G6P) and α-glucose 1-phosphate (αG1P). The chiral conformation of glucose, G6P, and αG1P plays an essential role in enzyme-mediated conversions. However, few techniques were able to give a direct view of the conformational changes from glucose to G6P and αG1P. Here, Raman optical activity (ROA) was used to elucidate the stereochemical evolution of glucose upon phosphorylation. ROA was found to be extremely sensitive to different phosphorylation sites. A characteristic ROA marker of (+)980 cm-1, originated from the phosphate group symmetric stretching vibration, is observed for αG1P with phosphorylation at chiral C1, while no corresponding ROA signal for G6P with phosphorylation at achiral C6 is observed. Phosphorylation-induced gauch-gauch (gg)/gauch-trans (gt) rotamer distribution changes can be sensitively probed by the sign of the ROA band around 1460 cm-1. A positive ROA band at 1465 cm-1 of glucose corresponds to a higher gt ratio, while a negative band at 1455 cm-1 of G6P suggests a dominant gg population, and the disappearance of this ROA band for αG1P indicates a nearly balanced gg/gt distribution. Meanwhile, the phosphorylation at C6 and C1 could cause dramatic reduction of the conformational flexibility of the adjacent C4-OH and C2-OH, respectively. These stereochemical changes revealed by ROA spectra offer a structural basis on the understanding of sugar phosphorylation from the perspective of chirality.

A highly selective and stable ZnO-ZrO2 solid solution catalyst for CO2 hydrogenation to methanol.

Although methanol synthesis via CO hydrogenation has been industrialized, CO2 hydrogenation to methanol still confronts great obstacles of low methanol selectivity and poor stability, particularly for supported metal catalysts under industrial conditions. We report a binary metal oxide, ZnO-ZrO2 solid solution catalyst, which can achieve methanol selectivity of up to 86 to 91% with CO2 single-pass conversion of more than 10% under reaction conditions of 5.0 MPa, 24,000 ml/(g hour), H2/CO2 = 3:1 to 4:1, 320° to 315°C. Experimental and theoretical results indicate that the synergetic effect between Zn and Zr sites results in the excellent performance. The ZnO-ZrO2 solid solution catalyst shows high stability for at least 500 hours on stream and is also resistant to sintering at higher temperatures. Moreover, no deactivation is observed in the presence of 50 ppm SO2 or H2S in the reaction stream.

A Short-Wavelength Raman Optical Activity Spectrometer with Laser Source at 457 nm for the Characterization of Chiral Molecules.

Developing a high-sensitivity Raman optical activity (ROA) spectrometer has been regarded as one of the great challenges in chiral science and technology. Herein, we report our recent progress on the development of a short-wavelength ROA (sw-ROA) spectrometer with the excitation line at 457 nm, which shows obviously improved signal-to-noise (S/N) ratio compared with the currently available 532 nm ROA spectrometer. This could be ascribed to the fifth-power of frequency dependence for ROA intensity together with the potential advantage of avoiding fluorescence for most molecules. The required laser power at the sample for being able to obtain a reliable ROA spectrum is less than 150 milliwatts (mW) for most samples. In the case of neat S-α-pinene sample, the ROA signal can be acquired with the laser power at sample as low as 5 mW with the total exposure time of 5 min. The concentration of S-α-pinene sample can be reduced to 10% (v/v) by diluting with ethanol. These results demonstrate the great potential of sw-ROA (457 nm) working with decreased laser power, shortened acquisition time, and lower sample concentration. The applicability of sw-ROA (457 nm) has also been demonstrated by measuring representative chiral samples, including carbohydrates, amino acids, protein in aqueous solution, and chiral organic molecule in organic solvents.

Roles of adsorption sites in electron transfer from CdS quantum dots to molecular catalyst cobaloxime studied by time-resolved spectroscopy.

Electron transfer from CdS quantum dots (QDs) to cobaloxime (Co(dmgH)2pyCl) is demonstrated by transient absorption spectroscopy (TAS), and further confirmed using photoluminescence (PL) techniques. The analysis of the PL quenching results offers a novel way to understand the roles of the surface adsorption sites of CdS QDs in the performance of charge transfer in the CdS QDs-cobaloxime hybrid system. Two types of quenching dynamics reveal that there are two different adsorption modes of cobaloxime on the CdS QD surface. When cobaloxime substitutes the surface capping ligands of CdS QDs under low cobaloxime concentrations, the transfer is nearly unfavorable for both the free and trapped electrons. When cobaloxime occupies the surface defect sites of the CdS QDs under high cobaloxime concentrations, the transfer of both the free and trapped electrons is very effective, with an extremely high quenching rate constant of ∼10(12) M(-1) s(-1). Therefore, controlling the molecular adsorption sites and adjusting the surface defect properties of semiconductor QDs provide a strategy to improve the electron transfer efficiency of the QDs-cobaloxime photocatalytic system.

Dual Extraction of Photogenerated Electrons and Holes from a Ferroelectric Sr0.5Ba0.5Nb2O6 Semiconductor.

The separation of photogenerated charges is a critical factor in photocatalysis. Recently, anomalous photovoltaic (APV) field effects (Voc ∼ 10(3) V/cm) in ferroelectrics, with their strong driving force for charge separation, have attracted much attention in photocatalysis and photoelectrocatalysis. However, it is still unknown whether photogenerated electrons and holes can be simultaneously extracted by the strong driving force toward the surface of ferroelectrics and can become available for surface reactions. This issue becomes critically important in photocatalysis because the surface reaction utilizes both the electrons and holes that reach the surface. In this work, a model lateral symmetric structure, metal/Sr0.5Ba0.5Nb2O6/metal (metal = Ag or Pt), as an electrode was fabricated. The dual extractions of photogenerated electrons and holes on the two opposite metal electrodes were achieved, as revealed by photovoltaic and ferroelectrical hysteresis measurements and photoassisted Kelvin probe force microscopy (KPFM). It was found that the high Schottky barriers of the two opposite Sr0.5Ba0.5Nb2O6-Pt electrodes are key factors that alter the two space charge regions (SCRs) by a poling effect. The resulting built-in electrical fields with parallel directions near both electrodes significantly enhance the charge separation ability. Our model unravels the driving force of charge separation in ferroelectric semiconductors, thus demonstrating the potential for highly efficient charge separation in photocatalysis.

Insights of the Crystallization Process of Molecular Sieve AlPO4-5 Prepared by Solvent-Free Synthesis.

Crystallization of AlPO4-5 with AFI structure under solvent-free conditions has been investigated. Attention was mainly focused on the characterization of the intermediate phases formed at the early stages during the crystallization. The development in the long-range ordering of the solid phases as a function of crystallization time was monitored by XRD, SEM, IR, UV-Raman, and MAS NMR techniques. Particularly, the UV-Raman spectroscopy was employed to obtain the information on the formation process of the framework. J-HMQC (27)Al/(31)P double-resonance NMR experiments were used to identify the P-O-Al bonded species in the intermediate phases. For the first time the P-O-Al bonded species in the intermediate phases can be correctly described through using this advanced NMR technique. The crystallization under solvent-free conditions appears to follow the pathway: The initial amorphous raw material is converted to an intermediate phase which has four-/six-membered ring species, then gradually transformed into crystalline AlPO4-5. This observation is not consistent with the common idea that the intermediate phase is the semicrystalline intermediates with a three-dimensional structure.