Mechanochemical Synthesis of α-halo Alkylboronic Esters.

α-halo alkylboronic esters, acting as ambiphilic synthons, play a pivotal role as versatile intermediates in fields like pharmaceutical science and organic chemistry. The sequential transformation of carbon-boron and carbon-halogen bonds into a broad range of carbon-X bonds allows for programmable bond formation, facilitating the incorporation of multiple substituents at a single position and streamlining the synthesis of complex molecules. Nevertheless, the synthetic potential of these compounds is constrained by limited reaction patterns. Additionally, the conventional methods often necessitate the use of bulk toxic solvents, exhibit sensitivity to air/moisture, rely on expensive metal catalysts, and involve extended reaction times. In this report, a ball milling technique is introduced that overcomes these limitations, enabling the external catalyst-free multicomponent coupling of aryl diazonium salts, alkenes, and simple metal halides. This approach offers a general and straightforward method for obtaining a diverse array of α-halo alkylboronic esters, thereby paving the way for the extensive utilization of these synthons in the synthesis of fine chemicals.

Reticular Synthesis of Hydrogen-Bonded Organic Frameworks and Their Derivatives via Mechanochemistry.

Rational synthesis of hydrogen-bonded organic frameworks (HOFs) with predicted structure has been a long-term challenge. Herein, by using the efficient, simple, low-cost, and scalable mechanosynthesis, we demonstrate that reticular chemistry is applicable to HOF assemblies based on building blocks with different geometry, connectivity, and functionality. The obtained crystalline HOFs show uniform nano-sized morphology, which is challenging or unachievable for conventional solution-based methods. Furthermore, the one-pot mechanosynthesis generated a series of Pd@HOF composites with noticeably different CO oxidation activities. In situ DRIFTS studies indicate that the most efficient composite, counterintuitively, shows the weakest CO affinity to Pd sites while the strongest CO affinity to HOF matrix, revealing the vital role of porous matrix to the catalytic performance. This work paves a new avenue for rational synthesis of HOF and HOF-based composites for broad application potential.

Isolated Square-Planar Copper Center in Boron Imidazolate Nanocages for Photocatalytic Reduction of CO2 to CO.

Photocatalytic reduction of CO2 to value-added fuel has been considered to be a promising strategy to reduce global warming and shortage of energy. Rational design and synthesis of catalysts to maximumly expose the active sites is the key to activate CO2 molecules and determine the reaction selectivity. Herein, we synthesize a well-defined copper-based boron imidazolate cage (BIF-29) with six exposed mononuclear copper centers for the photocatalytic reduction of CO2 . Theoretical calculations show a single Cu site including weak coordinated water delivers a new state in the conduction band near the Fermi level and stabilizes the *COOH intermediate. Steady-state and time-resolved fluorescence spectra show these Cu sites promote the separation of electron-hole pairs and electron transfer. As a result, the cage achieves solar-driven reduction of CO2 to CO with an evolution rate of 3334 µmol g-1 h-1 and a high selectivity of 82.6 %.

Synthesis of CeO2 assemblies through interaction with short-chain dicarboxylic acids under facile hydrothermal conditions.

CeO2 assemblies with various morphologies were synthesized via a facile hydrothermal method using short-chain dicarboxylic acids as the only added agent. It is demonstrated that the morphology of CeO2 assemblies depends on the chain-length of the dicarboxylic acids. The reaction with propanedioic acid (PA) results in durian-like ceria assemblies. Comparatively, ethanedioic acid (EA) tends to precipitate with Ce3+ at the beginning, and then guides the formation of lamellar octahedral assemblies. The catalytic performance towards CO oxidation of the as-synthesized CeO2 with different morphologies was investigated. Compared with lamellar octahedral assemblies, durian-like CeO2 assemblies showed better catalytic performance, giving complete CO conversion at 350 °C, due to its properties of unique oxygen vacancies, loosely packed pore structure and larger specific surface area.

Anchoring High-Concentration Oxygen Vacancies at Interfaces of CeO(2-x)/Cu toward Enhanced Activity for Preferential CO Oxidation.

Catalysts are urgently needed to remove the residual CO in hydrogen feeds through selective oxidation for large-scale applications of hydrogen proton exchange membrane fuel cells. We herein propose a new methodology that anchors high concentration oxygen vacancies at interface by designing a CeO2-x/Cu hybrid catalyst with enhanced preferential CO oxidation activity. This hybrid catalyst, with more than 6.1% oxygen vacancies fixed at the favorable interfacial sites, displays nearly 100% CO conversion efficiency in H2-rich streams over a broad temperature window from 120 to 210 °C, strikingly 5-fold wider than that of conventional CeO2/Cu (i.e., CeO2 supported on Cu) catalyst. Moreover, the catalyst exhibits a highest cycling stability ever reported, showing no deterioration after five cycling tests, and a super long-time stability beyond 100 h in the simulated operation environment that involves CO2 and H2O. On the basis of an arsenal of characterization techniques, we clearly show that the anchored oxygen vacancies are generated as a consequence of electron donation from metal copper atoms to CeO2 acceptor and the subsequent reverse spillover of oxygen induced by electron transfer in well controlled nanoheterojunction. The anchored oxygen vacancies play a bridging role in electron capture or transfer and drive molecule oxygen into active oxygen species to interact with the CO molecules adsorbed at interfaces, thus leading to an excellent preferential CO oxidation performance. This study opens a window to design a vast number of high-performance metal-oxide hybrid catalysts via the concept of anchoring oxygen vacancies at interfaces.

One-step calcination-free synthesis of multicomponent spinel assembled microspheres for high-performance anodes of li-ion batteries: a case study of MnCo(2)O(4).

Multicomponent spinel metal-oxide assembled mesoporous microspheres, promising anode materials for Li-ion batteries with superior electrochemical performance, are usually obtained using different kinds of precursors followed by high-temperature post-treatments. Nevertheless, high-temperature calcinations often cause primary particles to aggregate and coarsen, which may damage the assembled microsphere architectures, leading to deterioration of electrochemical performance. In this work, binary spinel metal-oxide assembled mesoporous microspheres MnCo2O4 were fabricated by one-step low-temperature solvothermal method through handily utilizing the redox reaction of nitrate and ethanol. This preparation method is calcination-free, and the resulting MnCo2O4 microspheres were surprisingly assembled by nanoparticles and nanosheets. Two kinds of MnCo2O4 crystal nucleus with different exposed facet of (1̅10) and (11̅2̅) could be responsible for the formation of particle-assembled and sheet-assembled microspheres, respectively. Profiting from the self-assembly structure with mesoporous features, MnCo2O4 microspheres delivered a high reversible capacity up to 722 mAh/g after 25 cycles at a current density of 200 mA/g and capacities up to 553 and 320 mAh/g after 200 cycles at a higher current density of 400 and 900 mA/g, respectively. Even at an extremely high current density of 2700 mA/g, the electrode still delivered a capacity of 403 mAh/g after cycling with the stepwise increase of current densities. The preparation method reported herein may provide hints for obtaining various advanced multicomponent spinel metal-oxide assembled microspheres such as CoMn2O4, ZnMn2O4, ZnCo2O4, and so on, for high-performance energy storage and conversion devices.

Targeted deposition of ZnO2 on brookite TiO2 nanorods towards high photocatalytic activity.

A novel heterostructure was first synthesized by directly depositing photocatalytic inert ZnO2 onto facet {201} of brookite nanorods. The heterostructure thus obtained was found to show a superior photocatalytic activity under UV-light irradiation. The exceptional photocatalytic performance was due to the band-structure match between ZnO2 and brookite as well as synergic charge accumulation by different facets of the brookite nanorods.

Synthesis of high-quality brookite TiO2 single-crystalline nanosheets with specific facets exposed: tuning catalysts from inert to highly reactive.

The brookite phase of TiO(2) is hardly prepared and rarely studied in comparison with the common anatase and rutile phases. In addition, there exist immense controversies over the cognition of the light-induced liveliness of this material. Here, a novel, low-basicity solution chemistry method was first used to prepare homogeneous high-quality brookite TiO(2) single-crystalline nanosheets surrounded with four {210}, two {101}, and two {201} facets. These nanosheets exhibited outstanding activity toward the catalytic degradation of organic contaminants superior even to that of Degussa P25, due to the exposure of high-energy facets and the effective suppression of recombination rates of photogenerated electrons and holes by these facets as the oxidative and reductive sites. In contrast, irregularly faceted phase-pure brookite nanoflowers and nanospindles were inactive in catalytic reactions. These results demonstrate that the photocatalytic activity of brookite TiO(2) is highly dependent upon its exposed facets, which offers a strategy for tuning the catalysts from inert to highly active through tailoring of the morphology and surface structure.