Tuning the Local Environment of Pt Species at CNT@MO2-x (M = Sn and Ce) Heterointerfaces for Boosted Alkaline Hydrogen Evolution.

As the most promising hydrogen evolution reaction (HER) electrocatalysts, platinum (Pt)-based catalysts still struggle with sluggish kinetics and expensive costs in alkaline media. Herein, we accelerate the alkaline hydrogen evolution kinetics by optimizing the local environment of Pt species and metal oxide heterointerfaces. The well-dispersed PtRu bimetallic clusters with adjacent MO2-x (M = Sn and Ce) on carbon nanotubes (PtRu/CNT@MO2-x) are demonstrated to be a potential electrocatalyst for alkaline HER, exhibiting an overpotential of only 75 mV at 100 mA cm-2 in 1 M KOH. The excellent mass activity of 12.3 mA µg-1Pt+Ru and specific activity of 32.0 mA cm-2ECSA at an overpotential of 70 mV are 56 and 64 times higher than those of commercial Pt/C. Experimental and theoretical investigations reveal that the heterointerfaces between Pt clusters and MO2-x can simultaneously promote H2O adsorption and activation, while the modification with Ru further optimizes H adsorption and H2O dissociation energy barriers. Then, the matching kinetics between the accelerated elementary steps achieved superb hydrogen generation in alkaline media. This work provides new insight into catalytic local environment design to simultaneously optimize the elementary steps for obtaining ideal alkaline HER performance.

Mechanism and Solution of Overcharge Effect in Lithium-Sulfur Batteries.

Increasing the sulfur cathode load is an important method for promoting the commercialization of lithium-sulfur batteries. However, there is a common problem of overcharging in high-loading experiments, which is rarely reported. In this work, it is believed that an insulating layer of S8 forms on the current collector surface, hindering electron exchange with polysulfides. Continuous external current input during layer formation can cause irreversible electrode changes and overcharging. The general solution is to provide nucleation centers with adsorption sites to promote the 3D growth of the insulated S8 , thus avoiding overcharging. In this work,  a solution is proposed by providing nucleation centers by gallium nitrate, by regulating the 3D growth of S8 away from the surface of the current collector to avoid overcharging and by improving battery performance.

An alternative synthetic approach for efficient catalytic conversion of syngas to ethanol.

Ethanol is an attractive end product and a versatile feedstock because a widespread market exists for its commercial use as a fuel additive or a potential substitute for gasoline. Currently, ethanol is produced primarily by fermentation of biomass-derived sugars, particularly those containing six carbons, but coproducts 5-carbon sugars and lignin remain unusable. Another major process for commercial production of ethanol is hydration of ethylene over solid acidic catalysts, yet not sustainable considering the depletion of fossil fuels. Catalytic conversion of synthetic gas (CO + H2) could produce ethanol in large quantities. However, the direct catalytic conversion of synthetic gas to ethanol remains challenging, and no commercial process exists as of today although the research has been ongoing for the past 90 years, since such the process suffers from low yield and poor selectivity due to slow kinetics of the initial C-C bond formation and fast chain growth of the C2 intermediates. This Account describes recent developments in an alternative approach for the synthesis of ethanol via synthetic gas. This process is an integrated technology consisting of the coupling of CO with methanol to form dimethyl oxalate and the subsequent hydrogenation to yield ethanol. The byproduct of the second step (methanol) can be separated and used in circulation as the feedstock for the coupling step. The coupling reaction of carbon monoxide for producing dimethyl oxalate takes place under moderate reaction conditions with high selectivity (∼95%), which ideally leads to a self-closing, nonwaste, catalytic cycling process. This Account also summarizes the progress on the development of copper-based catalysts for the hydrogenation reaction with remarkable efficiencies and stability. The unique lamellar structure and the cooperative effect between surface Cu(0) and Cu(+) species are responsible for the activity of the catalyst with high yield of ethanol (∼91%). The understanding of nature of valence states of Cu could also guide the rational design of Cu-based catalysts for other similar reactions, particularly for hydrogenation catalytic systems. In addition, by regulating the reaction condition and the surface structure of the catalysts, the products in the hydrogenation steps, such as ethanol, methyl glycolate, and ethylene glycol, could be tuned efficiently. This synthetic approach enables a more sustainable ethanol, methyl glycolate, and ethylene glycol synthesis in industry and greatly reduces the dependence on petroleum resources and the emission of the greenhouse gas.

Low-Cytotoxic Core-Sheath ZnO NWs@TiO2-xNy Triggered Piezo-photocatalytic Antibacterial Activity.

Sonophotodynamic antimicrobial therapy (SPDAT) is recognized as a highly efficient biomedical treatment option, known for its versatility and remarkable healing outcomes. Nevertheless, there is a scarcity of sonophotosensitizers that demonstrate both low cytotoxicity and exceptional antibacterial effectiveness in clinical applications. In this paper, a novel ZnO nanowires (NWs)@TiO2-xNy core-sheath composite was developed, which integrates the piezoelectric effect and heterojunction to build dual built-in electric fields. Remarkably, it showed superb antibacterial effectiveness (achieving 95% within 60 min against S. aureus and ∼100% within 40 min against E. coli, respectively) when exposed to visible light and ultrasound. Due to the continuous interference caused by light and ultrasound, the material's electrostatic equilibrium gets disrupted. The modification in electrical properties facilitates the composite's ability to attract bacterial cells through electrostatic forces. Moreover, Zn-O-Ti and Zn-N-Ti bonds formed at the interface of ZnO NWs@TiO2-xNy, further enhancing the dual internal electric fields to accelerate the excited carrier separation to generate more reactive oxygen species (ROS), and thereby boosting the antimicrobial performance. In addition, the TiO2 layer limited Zn2+ dissolution into solution, leading to good biocompatibility and low cytotoxicity. Lastly, we suggest a mechanistic model to offer practical direction for the future development of antibacterial agents that are both low in toxicity and high in efficacy. In comparison to the traditional photodynamic therapy systems, ZnO NWs@TiO2-xNy composites exhibit super piezo-photocatalytic antibacterial activity with low toxicity, which shows great potential for clinical application as an antibacterial nanomaterial.

Piezo-photocatalytic reduction of nitrates to N2 over silver dispersed on BaTiO3@TiO2.

This communication first achieved piezo-photocatalytic reduction of nitrates to N2 through designing an Ag2O/BaTiO3@TiO2 core-shell catalyst. The built-in electric field induced by piezoelectric polarization suppresses photoexcited carrier recombination, and simultaneously causes energy band tilting, leading to the generation of electrons with higher reducibility to directly trigger the NO3- reduction to ˙NO32-, even without hole scavengers.

Ethylene glycol: properties, synthesis, and applications.

Ethylene glycol (EG) is an important organic compound and chemical intermediate used in a large number of industrial processes (e.g. energy, plastics, automobiles, and chemicals). Indeed, owing to its unique properties and versatile commercial applications, a variety of chemical systems (e.g., catalytic and non-catalytic) have been explored for the synthesis of EG, particularly via reaction processes derived from fossil fuels (e.g., petroleum, natural gas, and coal) and biomass-based resources. This critical review describes a broad spectrum of properties of EG and significant advances in the prevalent synthesis and applications of EG, with emphases on the catalytic reactivity and reaction mechanisms of the main synthetic methodologies and applied strategies. We also provide an overview regarding the challenges and opportunities for future research associated with EG.

Room-temperature activation of the C-H bond in the dehydrogenation of ethane over a Cu/TiO2 catalyst.

A novel photocatalytic system of Cu/TiO2 for activation the C-H bond in the dehydrogenation of ethane to ethylene at room temperature is proposed. The optimized 1%-Cu/TiO2 catalyst achieved C2H6 conversion of 1.70%, C2H4 selectivity of 98.41%, and exhibited excellent stability. The active site Cuδ+ showed high dispersion on the TiO2 surface. Theoretical calculations and in situ diffuse reflectance infrared Fourier transform spectroscopy revealed a reaction mechanism: C2H6 is first activated by adsorption over the Cu4C/TiO2 catalyst with elongation of the C-H bond, attacked by h+/˙OH to form ethyl radicals, which are then converted to C2H4.

Synthesis of ethanol via syngas on Cu/SiO2 catalysts with balanced Cu0-Cu+ sites.

This paper describes an emerging synthetic route for the production of ethanol (with a yield of ~83%) via syngas using Cu/SiO(2) catalysts. The remarkable stability and efficiency of the catalysts are ascribed to the unique lamellar structure and the cooperative effect between surface Cu(0) and Cu(+) obtained by an ammonia evaporation hydrothermal method. Characterization results indicated that the Cu(0) and Cu(+) were formed during the reduction process, originating from well-dispersed CuO and copper phyllosilicate, respectively. A correlation between the catalytic activity and the Cu(0) and Cu(+) site densities suggested that Cu(0) could be the sole active site and primarily responsible for the activity of the catalyst. Moreover, we have shown that the selectivity for ethanol or ethylene glycol can be tuned simply by regulating the reaction temperature.

Highly selective hydrogenation of dimethyl oxalate to methyl glycolate and ethylene glycol over an amino-assisted Ru-based catalyst.

A Ru/NH2-MCM-41 catalyst was prepared via a coordination-assisted strategy for chemoselective hydrogenation of dimethyl oxalate with a high selectivity of methyl glycolate (ca. 100%) and ethylene glycol (>90%) at reaction temperatures of 343 K and 433 K, respectively. The amino groups help to anchor and form stable electron-rich Ru active sites, which accounts for the excellent CO bond activation and hydrogenation selectivity.

In-Situ Fabricating V2O5/TiO2-Carbon Heterojunction from Ti3C2 MXene as Highly Active Visible-Light Photocatalyst.

Titanium dioxide is a mainstream photocatalyst, but it still confronts great obstacles of poor visible light absorption and rapid recombination rate of photogenerated carriers. Herein, we describe the design of a highly active visible-light photocatalytic system of graphited carbon layers anchored V2O5/TiO2 heterojunctions derived from Ti3C2 MXene, which demonstrates about 4.58 and 2.79 times higher degradation activity of MB under visible light (λ > 420 nm) than pure V2O5 and TiO2-carbon. Combined with the characterization results, the formed V2O5/TiO2 heterojunction promotes the separation of photogenerated carriers, while the graphitized carbon derived from MXene acts as an electronic reservoir to enhance the absorption of visible light. The ESR results show that superoxide radicals and hydroxyl radicals are the main active species in the reaction system. Therefore, we propose a possible mechanism model to provide a feasible idea for the subsequent design of high-efficiency photocatalysts for environmental treatment.

Design of Organic-Free Superhydrophobic TiO2 with Ultraviolet Stability or Ultraviolet-Induced Switchable Wettability.

Superhydrophobic TiO2 with great application potential is mainly obtained by surface modification with low surface energy organics, which is easily degraded under sunlight irradiation, which results in the loss of superhydrophobic properties. Herein, we developed a room-temperature pulsed chemical vapor deposition (pulsed CVD) method to develop amorphous TiO2-deposited TiO2 nanoparticles. The ultraviolet stability/ultraviolet-induced reversible wettability switch had been simultaneously realized by different and controllable deposition cycles of amorphous TiO2. The superhydrophobic properties of the organic-free TiO2 were determined by the micrometer-nanometer-sub-nanometer multiscale structure, the multiscale pore structure, and the large Young's contact angle resulting from carboxylic acid adsorption. Also, we found that the adsorption rate and adsorption stability of oxygen and water at the surface oxygen vacancies were the key to facilitate the reversible switching between superhydrophilic and superhydrophobic states, which was well demonstrated by experimental characterization and theoretical simulation. In addition, we also found that the resistance of dense amorphous TiO2 films on the TiO2 surface to the migration of photogenerated electrons and holes was the key to maintain the stable superhydrophobic properties of superhydrophobic TiO2 under ultraviolet illumination. The powders were strongly ground and the coating surface was rubbed on the surface of the sandpaper, which still maintained superhydrophobic properties, providing favorable conditions for the application of superhydrophobic TiO2. This work modulates the ultraviolet stability and dark/ultraviolet-induced switchable superhydrophobicity/superhydrophilicity of coated TiO2 by simply adjusting the number of deposition times in a pulsed CVD process for the first time, thus contributing to the development of organic-free superhydrophobic TiO2.

The role of adsorbed oleylamine on gold catalysts during synthesis for highly selective electrocatalytic reduction of CO2 to CO.

The low-coordinated sites of electrocatalysts favour hydrogen evolution, while the edge sites are active for CO2 reduction. Oleylamine is used to stabilize nanoparticles by adsorbing on the low-coordinated sites. The hydrogen evolution reaction was dramatically suppressed and the FECO remained >93% from -0.4 to -0.8 V (vs. RHE) when oleylamine ligands existed on the surface of a gold catalyst. More H+ and electrons were involved in the CO evolution reaction, which changed the rate-limiting step from single-electron transfer to the chemical reaction step. The results establish that the surface-adsorbed surfactants during catalyst synthesis have an important effect on CO2 electrocatalytic reduction.

Morphology-controlled synthesis of CoMoO4 nanoarchitectures anchored on carbon cloth for high-efficiency oxygen oxidation reaction.

Novel CoMoO4 nanoarrays with different morphologies are anchored on a carbon cloth via a simple hydrothermal method by adjusting the Co/Mo atom ratio. The in situ growth and tight immobilization of the CoMoO4 nanocomposite on the carbon cloth can facilitate the electrolyte infiltration and electrons transfer rate at the contact interface. Therefore, the free-standing electrode of CoMoO4/carbon cloth with interconnected nanosheets shows superior electrocatalytic activity, and the overpotential of 286 mV is obtained at 15 mA cm-2 in alkaline solution. Moreover, the catalyst also exhibits a small Tafel slope of 67 mV dec-1 as well as good stability. The relationship between the active material morphology, contact interface and the electrocatalytic performance is also discussed. As the carbon cloth is commercially available, this simple but effective structural controlling method demonstrates a new large-scale practical electrode fabrication technique for high performance OER electrodes and large-scale water splitting.

Insight into the synergism between MnO2 and acid sites over Mn-SiO2@TiO2 nano-cups for low-temperature selective catalytic reduction of NO with NH3.

The rational synthesis of low-temperature catalysts with high catalytic activity and stability is highly desirable for the selective catalytic reduction of NO with NH3. Here we synthesized a Mn-SiO2/TiO2 nano-cup catalyst via the coating of the mesoporous TiO2 layers on SiO2 spheres and subsequent inlay of MnO2 nanoparticles in the narrow annulus. This catalyst exhibited superior catalytic SCR activities and stability for low-temperature selective catalytic reduction of NO with NH3, with NO conversion of ∼100%, N2 selectivity above 90% at a temperature ∼140 °C. The characterization results, such as BET, XRD, H2-TPR, O2/NH3-TPD and XPS, indicated that this nano-cup structure catalyst possesses high concentration and dispersion of Mn4+ active species, strong chemisorbed O- or O2 2- species and highly stable MnO X active components over the annular structures of the TiO2 shell and SiO2 sphere, and thus enhanced the low-temperature SCR performance.

Floatable superhydrophobic Ag2O photocatalyst without a modifier and its controllable wettability by particle size adjustment.

In this research, a controlling mechanism of particle size on the wettability of Ag2O particles is reported, and an interesting floatable Ag2O photocatalyst with superhydrophobicity and superoleophilicity is prepared based on this mechanism. Stable superhydrophobic and superhydrophilic Ag2O without a low-surface-energy modifier can be obtained only by adjusting its particle size, and its wettability can switch mutually by changing the particle size. The wettability of Ag2O converts from superhydrophilic to hydrophobic when the average particle size is more than 1.08 µm. The operation parameters of the Ag2O crystallization process significantly influence the wettability of the Ag2O particles. The obtained superhydrophobic Ag2O floated on the water surface, and exhibited excellent photodegradation performance with various floating oils. This attractive superhydrophobic Ag2O photocatalyst is promising for practical applications, and provides a strategy for the development of functional photocatalysts and superhydrophobic materials.

A copper-phyllosilicate core-sheath nanoreactor for carbon-oxygen hydrogenolysis reactions.

Hydrogenolysis of carbon-oxygen bonds is a versatile synthetic tool in organic synthesis. Copper-based catalysts have been intensively explored as the copper sites account for the highly selective hydrogenation of carbon-oxygen bonds. However, the inherent drawback of conventional copper-based catalysts is the deactivation by metal-particle growth and unstable surface Cu(0) and Cu(+) active species in the strongly reducing hydrogen and oxidizing carbon-oxygen atmosphere. Here we report the superior reactivity of a core (copper)-sheath (copper phyllosilicate) nanoreactor for carbon-oxygen hydrogenolysis of dimethyl oxalate with high efficiency (an ethanol yield of 91%) and steady performance (>300 h at 553 K). This nanoreactor, which possesses balanced and stable Cu(0) and Cu(+) active species, confinement effects, an intrinsically high surface area of Cu(0) and Cu(+) and a unique tunable tubular morphology, has potential applications in high-temperature hydrogenation reactions.