Mesoporous TiO2 Single-Crystal Particles from Controlled Crystallization-Driven Mono-Micelle Assembly as an Efficient Photocatalyst.

Mesoporous materials with crystalline frameworks have been widely explored in many fields due to their unique structure and crystalline feature, but accurate manipulations over crystalline scaffolds, mainly composed of uncontrolled polymorphs, are still lacking. Herein, we explored a controlled crystallization-driven monomicelle assembly approach to construct a type of uniform mesoporous TiO2 particles with atomically aligned single-crystal frameworks. The resultant mesoporous TiO2 single-crystal particles possess an angular shape ∼80 nm in diameter, good mesoporosity (a high surface area of 112 m2 g-1 and a mean pore size at 8.3 nm), and highly oriented anatase frameworks. By adjusting the evaporation rate during assembly, such a facile solution-processed strategy further enables the regulation of the particle size and mesopore size without the destruction of the oriented crystallites. Such a combination of ordered mesoporosity and crystalline orientation provides both effective mass and charge transportation, leading to a significant increase in the hydrogen generation rate. A maximum hydrogen evolution rate of 12.5 mmol g-1 h-1 can be realized, along with great stability under solar light. Our study is envisaged to extend the possibility of mesoporous single crystal growth to a range of functional ceramics and semiconductors toward advanced applications.

Boosted Oxygen Kinetics of Hierarchically Mesoporous Mo2C/C for High-current-density Zn-air Battery.

The high-current-density Zn-air battery shows big prospects in next-generation energy technologies, while sluggish O2 reaction and diffusion kinetics barricade the applications. Herein, the sequential assembly is innovatively demonstrated for hierarchically mesoporous molybdenum carbides/carbon microspheres with a tunable thickness of mesoporous carbon layers (Meso-Mo2C/C-x, where x represents the thickness). The optimum Meso-Mo2C/C-14 composites (≈2 µm in diameter) are composed of mesoporous nanosheets (≈38 nm in thickness), which possess bilateral mesoporous carbon layers (≈14 nm in thickness), inner Mo2C/C layers (≈8 nm in thickness) with orthorhombic Mo2C nanoparticles (≈2 nm in diameter), a high surface area of ≈426 m2 g-1, and open mesopores (≈6.9 nm in size). Experiments and calculations corroborate the hierarchically mesoporous Mo2C/C can enhance hydrophilicity for supplying sufficient O2, accelerate oxygen reduction kinetics by highly-active Mo2C and N-doped carbon sites, and facilitate O2 diffusion kinetics over hierarchically mesopores. Therefore, Meso-Mo2C/C-14 outputs a high half-wave potential (0.88 V vs RHE) with a low Tafel slope (51 mV dec-1) for oxygen reduction. More significantly, the Zn-air battery delivers an ultrahigh power density (272 mW cm-2), and an unprecedented 100 h stability at a high-current-density condition (100 mA cm-2), which is one of the best performances.

Surface Stretching Enables Highly Disordered Graphitic Domains for Ultrahigh Rate Sodium Storage.

Hard carbons (HCs) with high sloping capacity are considered as the leading candidate anode for sodium-ion batteries (SIBs); nevertheless, achieving basically complete slope-dominated behavior with high rate capability is still a big challenge. Herein, the synthesis of mesoporous carbon nanospheres with highly disordered graphitic domains and MoC nanodots modification via a surface stretching strategy is reported. The MoOx surface coordination layer inhibits the graphitization process at high temperature, thus creating short and wide graphite domains. Meanwhile, the in situ formed MoC nanodots can greatly promote the conductivity of highly disordered carbon. Consequently, MoC@MCNs exhibit an outstanding rate capacity (125 mAh g-1 at 50 A g-1 ). The "adsorption-filling" mechanism combined with excellent kinetics is also studied based on the short-range graphitic domains to reveal the enhanced slope-dominated capacity. The insight in this work encourages the design of HC anodes with dominated slope capacity toward high-performance SIBs.

Self-Assembly of Ir-Based Nanosheets with Ordered Interlayer Space for Enhanced Electrocatalytic Water Oxidation.

Iridium (Ir)-based electrocatalysts are widely explored as benchmarks for acidic oxygen evolution reactions (OERs). However, further enhancing their catalytic activity remains challenging due to the difficulty in identifying active species and unfavorable architectures. In this work, we synthesized ultrathin Ir-IrOx/C nanosheets with ordered interlayer space for enhanced OER by a nanoconfined self-assembly strategy, employing block copolymer formed stable end-merged lamellar micelles. The interlayer distance of the prepared Ir-IrOx/C nanosheets was well controlled at ∼20 nm and Ir-IrOx nanoparticles (∼2 nm) were uniformly distributed within the nanosheets. Importantly, the fabricated Ir-IrOx/C electrocatalysts display one of the lowest overpotential (η) of 198 mV at 10 mA cm-2geo during OER in an acid medium, benefiting from their features of mixed-valence states, rich electrophilic oxygen species (O(II-δ)-), and favorable mesostructured architectures. Both experimental and computational results reveal that the mixed valence and O(II-δ)- moieties of the 2D mesoporous Ir-IrOx/C catalysts with a shortened Ir-O(II-δ)- bond (1.91 Å) is the key active species for the enhancement of OER by balancing the adsorption free energy of oxygen-containing intermediates. This strategy thus opens an avenue for designing high performance 2D ordered mesoporous electrocatalysts through a nanoconfined self-assembly strategy for water oxidation and beyond.

Controllable States and Porosity of Cu-Carbon for CO2 Electroreduction to Hydrocarbons.

The electrocatalytic carbon dioxide reduction reaction (CO2 RR) to value-added chemical products is an effective strategy for both greenhouse effect mitigation and high-density energy storage. However, controllable manipulation of the oxidation state and porous structure of Cu-carbon based catalysts to achieve high selectivity and current density for a particular product remains very challenging. Herein, a strategy derived from Cu-based metal-organic frameworks (MOFs) for the synthesis of controllable oxidation states and porous structure of Cu-carbon (Cu-pC, Cu2 O-pC, and Cu2 O/Cu-pC) is demonstrated. By regulating oxygen partial pressure during the annealing process, the valence state of the Cu and mesoporous structures of surrounding carbon are changed, leads to the different selectivity of products. Cu2 O/CuO-pC with the higher oxidation state exhibits FEC2H4 of 65.12% and a partial current density of -578 mA cm-2 , while the Cu2 O-pC shows the FECH4 over 55% and a partial current density exceeding -438 mA cm-2 . Experimental and theoretical studies indicate that porous carbon-coated Cu2 O structures favor the CH4 pathway and inhibit the hydrogen evolution reaction. This work provides an effective strategy for exploring the influence of the various valence states of Cu and mesoporous carbon structures on the selectivity of CH4 and C2 H4 products in CO2 RR.

Streamlined Mesoporous Silica Nanoparticles with Tunable Curvature from Interfacial Dynamic-Migration Strategy for Nanomotors.

Streamlined architectures with a low fluid-resistance coefficient have been receiving great attention in various fields. However, it is still a great challenge to synthesize streamlined architecture with tunable surface curvature at the nanoscale. Herein, we report a facile interfacial dynamic migration strategy for the synthesis of streamlined mesoporous nanotadpoles with varied architectures. These tadpole-like nanoparticles possess a big streamlined head and a slender tail, which exhibit large inner cavities (75-170 nm), high surface areas (424-488 m2 g-1), and uniform mesopore sizes (2.4-3.2 nm). The head curvature of the streamlined mesoporous nanoparticles can be well-tuned from ∼2.96 × 10-2 to ∼5.56 × 10-2 nm-1, and the tail length can also be regulated from ∼30 to ∼650 nm. By selectively loading the Fe3O4 catalyst in the cavity of the streamlined silica nanotadpoles, the H2O2-driven mesoporous nanomotors were designed. The mesoporous nanomotors with optimized structural parameters exhibit outstanding directionality and a diffusion coefficient of 8.15 µm2 s-1.

Precisely Designed Mesoscopic Titania for High-Volumetric-Density Pseudocapacitance.

Surface redox pseudocapacitance, which enables short charging times and high power delivery, is very attractive in a wide range of sites. To achieve maximized specific capacity, nanostructuring of active materials with high surface area is indispensable. However, one key limitation for capacitive materials is their low volumetric capacity due to the low tap density of nanomaterials. Here, we present a promising mesoscale TiO2 structure with precisely controlled mesoporous frameworks as a high-density pseudocapacitive model system. The dense-packed mesoscopic TiO2 in micrometer size offers a high accessible surface area (124 m2 g-1) and radially aligned mesopore channels, but high tap density (1.7 g cm-3) that is much higher than TiO2 nanoparticles (0.47 g cm-3). As a pseudocapacitive sodium-ion storage anode, the precisely designed mesoscopic TiO2 model achieved maximized gravimetric capacity (240 mAh g-1) and volumetric capacity (350 mAh cm-3) at 0.025 A g-1. Such a designed pseudocapacitive mesostructure further realized a commercially comparable areal capacity (2.1 mAh cm-2) at a high mass loading of 9.47 mg cm-2. This mesostructured electrode that enables fast sodiation in dense nanostructures has implications for high-power applications, fast-charging devices, and pseudocapacitive electrode design.

Anodic Hydrazine Oxidation Assists Energy-Efficient Hydrogen Evolution over a Bifunctional Cobalt Perselenide Nanosheet Electrode.

Water electrolysis is a promising source of hydrogen; however, technological challenges remain. Intensive efforts have focused on developing highly efficient and earth-abundant electrocatalysts for water splitting. An effective strategy is proposed, using a bifunctional tubular cobalt perselenide nanosheet electrode, in which the sluggish oxygen evolution reaction is substituted with anodic hydrazine oxidation so as to assist energy-efficient hydrogen production. Specifically, this electrode produces a current density of 10 mA cm-2 at -84 mV for hydrogen evolution and -17 mV for hydrazine oxidation in 1.0 m KOH and 0.5 m hydrazine electrolyte. An ultralow cell voltage of only 164 mV is required to generate a current density of 10 mA cm-2 for 14 hours of stable water electrolysis.

Stepwise Monomicelle Assembly for Highly Ordered Mesoporous TiO2 Membranes with Precisely Tailored Mesophase and Porosity.

Mesoporous materials with crystalline frameworks have been acknowledged as very attractive materials in various applications. Nevertheless, due to the cracking issue during crystallization and incompatible hydrolysis and assembly, the precise control for crystalline mesoscale membranes is quite infertile. Herein, we presented an ingenious stepwise monomicelle assembly route for the syntheses of highly ordered mesoporous crystalline TiO2 membranes with delicately controlled mesophase, mesoporosity, and thickness. Such a process involves the preparation of monomicelle hydrogels and follows self-assembly by stepwise solvent evaporation, which enables the sensitive hydrolysis of TiO2 oligomers and dilatory micelle assembly to be united. In consequence, the fabricated mesoporous TiO2 membranes exhibit a broad flexibility, including tunable ordered mesophases (worm-like, hexagonal p6mm to body-centered cubic Im3̅m), controlled mesopore sizes (3.0-8.0 nm), and anatase grain sizes (2.3-8.4 nm). Besides, such mesostructured crystalline TiO2 membranes can be extended to diverse substrates (Ti, Ag, Si, FTO) with tailored thickness. The great mesoporosity of the in situ fabricated mesoscopic membranes also affords excellent pseudocapacitive behavior for sodium ion storage. This study underscores a novel pathway for balancing the interaction of precursors and micelles, which could have implications for synthesizing crystalline mesostructures in higher controllability.

A Zeolitic-Imidazole Framework-Derived Trifunctional Electrocatalyst for Hydrazine Fuel Cells.

Hydrazine fuel cells are promising sustainable power sources. However, the high price and limited reserves of noble metal catalysts that promote the sluggish cathodic and anodic electrochemical reactions hinder their practical applications. Reflecting the enhanced diffusion and improved kinetics of nanostructured non-noble metal electrocatalysts, we report an efficient zeolitic-imidazole framework-derived trifunctional electrocatalyst for hydrazine oxidation, oxygen, and hydrogen peroxide reduction. Experimental results and theoretical calculations corroborate that the nanocarbon architecture with abundant Co-N species enhances the electronic interaction and optimizes the energy barriers of anodic hydrazine oxidation and cathodic oxygen reduction. The resulting assembled hydrazine-oxygen fuel cell yields a cell voltage and power density of 0.74 V and 20.5 mW cm-2, respectively. Moreover, benefiting from the liquid-liquid diffusion, the hydrazine-hydrogen peroxide cell shows a boosted cell voltage and power density, corresponding to 1.68 V and 41.0 mW cm-2. This work offers a highly active non-noble metal multifunctional electrocatalyst with a pioneering diffusion philosophy in the liquid electrochemical cells.

Rational Design of Cobalt-Iron Selenides for Highly Efficient Electrochemical Water Oxidation.

Exploring active, stable, earth-abundant, low-cost, and high-efficiency electrocatalysts is highly desired for large-scale industrial applications toward the low-carbon economy. In this study, we apply a versatile selenizing technology to synthesize Se-enriched Co1-xFexSe2 catalysts on nickel foams for oxygen evolution reactions (OERs) and disclose the relationship between the electronic structures of Co1-xFexSe2 (via regulating the atom ratio of Co/Fe) and their OER performance. Owing to the fact that the electron configuration of the Co1-xFexSe2 compounds can be tuned by the incorporated Fe species (electron transfer and lattice distortion), the catalytic activity can be adjusted according to the Co/Fe ratios in the catalyst. Moreover, the morphology of Co1-xFexSe2 is also verified to strongly depend on the Co/Fe ratios, and the thinner Co0.4Fe0.6Se2 nanosheets are obtained upon selenization treatment, in which it allows more active sites to be exposed to the electrolyte, in turn promoting the OER performance. The Co0.4Fe0.6Se2 nanosheets not only exhibit superior OER performance with a low overpotential of 217 mV at 10 mA cm-2 and a small Tafel slope of 41 mV dec-1 but also possess ultrahigh durability with a dinky degeneration of 4.4% even after 72 h fierce water oxidation test in alkaline solution, which outperforms the commercial RuO2 catalyst. As expected, the Co0.4Fe0.6Se2 nanosheets have shown great prospects for practical applications toward water oxidation.

"Cuju"-Structured Iron Diselenide-Derived Oxide: A Highly Efficient Electrocatalyst for Water Oxidation.

Electrocatalysts with outstanding performance have been highly desired toward exploration of new energy storage and conversion devices/systems as well as making an efficient and eco-friendly utilization of green energy. In this study, we composed an iron-based binary diselenide-derived oxide (Fe-SDO) with a facile one-step hydrothermal method to utilize the earth-abundant iron and the probably prosperous catalytic performance of metal-selenides compounds. The catalyst exhibits an overpotential of 226 mV at a current density of 10 mA/cm2, a Tafel slope of 41 mV dec-1, and robust durability after catalyzing vigorous OER for 36 h constantly. Through several analytical methods conducted before and after the oxygen evolution reaction activation on FeSe2 it was discovered that such catalyst possessed a morphology as "Cuju"-like balls with porosity inside in which we explored the vacancy defects and lattice distortion that play significant roles in generating the high electrocatalytic performance of our proposed catalyst by inducing remarkable electron conductivity in the porous Cuju balls (a Chinese traditional football). Throughout our work the superb electrocatalyst performance of the iron-based compounds was demonstrated, and subsequently the underlying reason for such electrocatalyst performance was addressed, which may push boundaries for the exploration of iron-based compounds as OER catalyst and large-scale commercial application of such compounds in the future.