Highly selective oxidation of benzene to phenol with air at room temperature promoted by water.

Phenol is one of the most important fine chemical intermediates in the synthesis of plastics and drugs with a market size of ca. $30b1 and the commercial production is via a two-step selective oxidation of benzene, requiring high energy input (high temperature and high pressure) in the presence of a corrosive acidic medium, and causing serious environmental issues2-5. Here we present a four-phase interface strategy with well-designed Pd@Cu nanoarchitecture decorated TiO2 as a catalyst in a suspension system. The optimised catalyst leads to a turnover number of 16,000-100,000 for phenol generation with respect to the active sites and an excellent selectivity of ca. 93%. Such unprecedented results are attributed to the efficient activation of benzene by the atomically Cu coated Pd nanoarchitecture, enhanced charge separation, and an oxidant-lean environment. The rational design of catalyst and reaction system provides a green pathway for the selective conversion of symmetric organic molecules.

A Z-Scheme Heterojunctional Photocatalyst Engineered with Spatially Separated Dual Redox Sites for Selective CO2 Reduction with Water: Insight by In Situ µs-Transient Absorption Spectra.

Solar-driven CO2 reduction by water with a Z-scheme heterojunction affords an avenue to access energy storage and to alleviate greenhouse gas (GHG) emissions, yet the separation of charge carriers and the integrative regulation of water oxidation and CO2 activation sites remain challenging. Here, a BiVO4 /g-C3 N4 (BVO/CN) Z-scheme heterojunction as such a prototype is constructed by spatially separated dual sites with CoOx clusters and imidazolium ionic liquids (IL) toward CO2 photoreduction. The optimized CoOx -BVO/CN-IL delivers an ≈80-fold CO production rate without H2 evolution compared with urea-C3 N4 counterpart, together with nearly stoichiometric O2 gas produced. Experimental results and DFT calculations unveil the cascade Z-scheme charge transfer and subsequently the prominent redox co-catalysis by CoOx and IL for holes-H2 O oxidation and electrons-CO2 reduction, respectively. Moreover, in situ µs-transient absorption spectra clearly show the function of each cocatalyst and quantitatively reveal that the resulting CoOx -BVO/CN-IL reaches up to the electron transfer efficiency of 36.4% for CO2 reduction, far beyond those for BVO/CN (4.0%) and urea-CN (0.8%), underlining an exceptional synergy of dual reaction sites engineering. This work provides deep insights and guidelines for the rational design of highly efficient Z-scheme heterojunctions with precise redox catalytic sites toward solar fuel production.

Investigation on the Fatigue Crack Propagation of Medium-Entropy Alloys with Heterogeneous Microstructures.

The behavior and the mechanism of fatigue crack propagation in CrCoNi medium-entropy alloys (MEAs) with heterogeneous microstructures were investigated in this paper. After cold-rolling and recrystallization annealing at different temperatures and times, five sets of heterostructured specimens were acquired with different recrystallization levels. Then, the structure characterizations of these five sets of specimens were carried out by nanoindentation testing and electron back-scatter diffraction (EBSD) mapping. Finally, the fatigue crack propagation tests were conducted on single edge crack specimens of these different heterogeneous microstructures. The experimental results indicate that the crack propagation rates of specimens with partial recrystallization microstructures are higher than those with complete recrystallization microstructures, and the effect on fatigue crack thresholds of these specimens is the opposite. The fatigue cracks grow along the slip planes or twin boundaries in recrystallization grains (RGs), which induced crack deflections and the roughness-induced crack closure effect. For this reason, the area percentage of recrystallization and the grain size of RGs have a great effect on the value of the fatigue crack growth threshold.

Modification of Covalent Triazine-Based Frameworks for Photocatalytic Hydrogen Generation.

The conversion of solar energy and water to hydrogen via semiconductor photocatalysts is one of the efficient strategies to mitigate the energy and environmental crisis. Conjugated polymeric photocatalysts have advantages over their inorganic counterparts. Their molecular structures, band structures, and electronic properties are easily tunable through molecular engineering to extend their spectral response ranges, improve their quantum efficiencies, and enhance their hydrogen evolution rates. In particular, covalent triazine-based frameworks (CTFs) present a strong potential for solar-driven hydrogen generation due to their large continuous π-conjugated structure, high thermal and chemical stability, and efficient charge transfer and separation capability. Herein, synthesis strategies, functional optimization, and applications in the photocatalytic hydrogen evolution of CTFs since the first investigation are reviewed. Finally, the challenges of hydrogen generation for CTFs are summarized, and the direction of material modifications is proposed.

In Situ Investigation of Charge Performance in Anatase TiO2 Powder for Methane Conversion by Vis-NIR Spectroscopy.

The intrinsic behavior of photogenerated charges and reactions with chemicals are key for a photocatalytic process. To observe these basic steps is of great importance. Here we present a reliable and robust system to monitor these basic steps in powder photocatalysts, and more importantly to elucidate the key issue in photocatalytic methane conversion over the benchmark catalyst TiO2. Under constant excitation, the absorption signal across the NIR region was demonstrated to be dominated by photoexcited electrons, the absorption of photoexcited holes increases toward shorter wavelengths in the visible region, and the overall shapes of the photoinduced absorption spectra obtained using the system demonstrated in the present work are consistent with widely accepted transient absorption results. Next, in situ measurements provide direct experimental evidence that the initial step of methane activation over TiO2 involves oxidation by photoexcited holes. It is calculated that 90 ± 6% of photoexcited electrons are scavenged by O2 (in dry air), 61 ± 9% of photoexcited holes are scavenged by methane (10% in argon), and a similar amount of photoexcited electrons can be scavenged by O2 even when the O2 concentration is reduced by a factor of 10. The present results suggest that O2 is much more easily activated in comparison to methane over anatase TiO2, which rationalizes the much higher methane/O2 ratio frequently used in practice in comparison to that required stoichiometrically for photocatalytic production of value-added chemicals via methane oxidation with oxygen. In addition, methanol (a preferable product of methane oxidation) is much more readily oxidized than methane over anatase TiO2.

Rational Design of High-Concentration Ti3+ in Porous Carbon-Doped TiO2 Nanosheets for Efficient Photocatalytic Ammonia Synthesis.

Photocatalytic ammonia synthesis is exciting but quite challenging with a very moderate yield at present. One of the greatest challenges is to develop highly active centers in a photocatalyst for N2 reduction under ambient conditions. Herein, porous carbon-doped anatase TiOx (C-TiOx ) nanosheets with high-concentration active sites of Ti3+ are presented, which are produced by layered Ti3 SiC2 through a reproducible bottom-up approach. It is shown that the high-concentration Ti3+ sites are the major species for the significant increase in N2 photoreduction activity by the C-TiOx . Such bottom-up substitutional doping of C into TiO2 is responsible for both visible absorption and generation of Ti3+ concentration. Together with the porous nanosheets morphology and the loading of a Ru/RuO2 nanosized cocatalyst for enhanced charge separation and transfer, the optimal C-TiOx with a Ti3+ /Ti4+ ratio of 72.1% shows a high NH3 production rate of 109.3 µmol g-1 h-1 under visible-light irradiation and a remarkable apparent quantum efficiency of 1.1% at 400 nm, which is the highest compared to all TiO2 -based photocatalysts at present.

From UV to NIR: A Full-Spectrum Metal-Free Photocatalyst for Efficient Polymer Synthesis in Aqueous Conditions.

Photo-mediation offers unparalleled spatiotemporal control over controlled radical polymerizations (CRP). Photo-induced electron/energy transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization is particularly versatile owing to its oxygen tolerance and wide range of compatible photocatalysts. In recent years, broadband- and near-infrared (NIR)-mediated polymerizations have been of particular interest owing to their potential for solar-driven chemistry and biomedical applications. In this work, we present the first example of a novel photocatalyst for both full broadband- and NIR-mediated CRP in aqueous conditions. Well-defined polymers were synthesized in water under blue, green, red, and NIR light irradiation. Exploiting the oxygen tolerant and aqueous nature of our system, we also report PET-RAFT polymerization at the microliter scale in a mammalian cell culture medium.

Synergistic oxygen substitution and heterostructure construction in polymeric semiconductors for efficient water splitting.

Herein, we present a synergistic oxygen-substitution and heterostructure construction strategy to produce a two-dimensional oxygenated-triazine-heptazine-conjugated carbon nitride nanoribbon (TOH-CN). The TOH-CN was proved to have an internal donor-acceptor heterostructure that could promote interfacial charge separation and transport, while the oxygen substitution effect modulated the nanoribbon morphology with increased surface/edge active sites and tuned the electronic structure to extend visible-light absorption as well as to improve band structure alignment. Benefiting from these advantages, the TOH-CN served as an efficient bifunctional photocatalyst for both H2 and O2 evolution under visible-light irradiation, exhibiting a 16 times higher photocatalytic H2 evolution rate than that of its melon-based carbon nitride (g-C3N4) counterpart, and a remarkable apparent quantum yield of 7.9% at 420 nm. The O2 evolution rate was 6 times higher than that of g-C3N4, even much higher than those of most bifunctional carbon nitride-based photocatalysts. The developed synergistic strategy of oxygen substitution and heterostructure construction will provide an alternative route for the synthesis of efficient polymeric semiconductors toward efficient solar-to-chemical conversion.

Platinum- and CuOx -Decorated TiO2 Photocatalyst for Oxidative Coupling of Methane to C2 Hydrocarbons in a Flow Reactor.

Oxidative coupling of methane (OCM) is considered one of the most promising catalytic technologies to upgrade methane. However, C2 products (C2 H6 /C2 H4 ) from conventional methane conversion have not been produced commercially owing to competition from overoxidation and carbon accumulation at high temperatures. Herein, we report the codeposition of Pt nanoparticles and CuOx clusters on TiO2 (PC-50) and use of the resulting photocatalyst for OCM in a flow reactor operated at room temperature under atmospheric pressure for the first time. The optimized Cu0.1 Pt0.5 /PC-50 sample showed a highest yield of C2 product of 6.8 µmol h-1 at a space velocity of 2400 h-1 , more than twice the sum of the activity of Pt/PC-50 (1.07 µmol h-1 ) and Cu/PC-50 (1.9 µmol h-1 ), it might also be the highest among photocatalytic methane conversions reported so far under atmospheric pressure. A high C2 selectivity of 60 % is also comparable to that attainable by conventional high-temperature (>943 K) thermal catalysis. It is proposed that Pt functions as an electron acceptor to facilitate charge separation, while holes could transfer to CuOx to avoid deep dehydrogenation and the overoxidation of C2 products.

Key factors affecting photoelectrochemical performance of g-C3N4 polymer films.

We investigated the relationship between crystallinity, deep trap states and PEC performance of g-C3N4 photoelectrodes. Long-lived charge carriers were present in the more poorly crystalline samples, due to deeper trap states, which inversely correlated with photoelectrochemical performance. The charge diffusion length in a compact g-C3N4 film was determined to be ca. 1000 nm.

Dimension-Matched Zinc Phthalocyanine/BiVO4 Ultrathin Nanocomposites for CO2 Reduction as Efficient Wide-Visible-Light-Driven Photocatalysts via a Cascade Charge Transfer.

Cascade charge transfer was realized by a H-bond linked zinc phthalocyanine/BiVO4 nanosheet (ZnPc/BVNS) composite, which subsequently works as an efficient wide-visible-light-driven photocatalyst for converting CO2 into CO and CH4 , as shown by product analysis and 13 C isotopic measurement. The optimized ZnPc/BVNS nanocomposite exhibits a ca. 16-fold enhancement in the quantum efficiency compared with the reported BiVO4 nanoparticles at the excitation of 520 nm with an assistance of 660 nm photons. Experimental and theoretical results show the exceptional activities are attributed to the rapid charge separation by a cascade Z-scheme charge transfer mechanism formed by the dimension-matched ultrathin (ca. 8 nm) heterojunction nanostructure. The central Zn2+ in ZnPc could accept the excited electrons from the ligand and then provide a catalytic function for CO2 reduction. This Z-scheme is also feasible for other MPc, such as FePc and CoPc, together with BVNS.

Ultrasensitive On-Site Detection of Biological Active Ricin in Complex Food Matrices Based on Immunomagnetic Enrichment and Fluorescence Switch-On Nanoprobe.

Ricin is a highly toxic protein largely existing in castor beans, which could be used as a warfare agent due to its unique properties. As a deadenylase, inactivation of ricin means a loss of its toxic threat. Therefore, developing simple, accurate, and sensitive on-site detection of biologically active ricin in wide types of complex matrices is most valuable. Here, antifouling polymer brush modified magnetic beads were prepared first and post modified with ricin monoclonal antibody (the MB@P(C-H)-mAbricin) to efficiently capture ricin from various foods and biological matrices. Active ricin obtained in this manner were sequentially determined by a new designed AuNP/QDs nanoassembly. In this double strand oligodeoxynucleotides (dsODN) linked core-satellite nanoprobe, the fluorescence of satellite QDs was extensively quenched by AuNPs due to the dipole-metal interaction. Active ricin can react with its specific depurination substrates which had been inserted in the dsODN linkers. This reaction would trigger the separation of QDs from Au cores by cutting multiple adenines, and then result in the restoration of QDs fluorescence. By coupling with the magnetic enrichment, this AuNP/QDs nanoprobe provided a qualitative result for active ricin in the range from 10.0 to 100.0 ng mL-1 with the limit of detection as low as 7.46 ng mL-1. Compared with previously proposed methods, this on-site detection strategy offered an easy to handle on-site test for trace amounts of active ricin in a wide range of complex matrices.

Nanoporous Carbon: Liquid-Free Synthesis and Geometry-Dependent Catalytic Performance.

Nanostructured carbons with different pore geometries are prepared with a liquid-free nanocasting method. The method uses gases instead of liquid to disperse carbon precursors, leach templates, and remove impurities, minimizing synthetic procedures and the use of chemicals. The method is universal and demonstrated by the synthesis of 12 different porous carbons with various template sources. The effects of pore geometries in catalysis can be isolated and investigated. Two of the resulted materials with different pore geometries are studied as supports for Ru clusters in the hydrogenolysis of 5-hydroxymethylfurfural (HMF) and electrochemical hydrogen evolution (HER). The porous carbon-supported Ru catalysts outperform commercial ones in both reactions. It was found that Ru on bottleneck pore carbon shows a highest yield in hydrogenolysis of HMF to 2,5-dimethylfuran (DMF) due to a better confinement effect. A wide temperature operation window from 110 to 140 °C, with over 75% yield and 98% selectivity of DMF, has been achieved. Tubular pores enable fast charge transfer in electrochemical HER, requiring only 16 mV overpotential to reach current density of 10 mA·cm-2.

Tunable Covalent Triazine-Based Frameworks (CTF-0) for Visible-Light-Driven Hydrogen and Oxygen Generation from Water Splitting.

Covalent triazine-based frameworks (CTFs), a group of semiconductive polymers, have been identified for photocatalytic water splitting recently. Their adjustable band gap and facile processing offer great potential for discovery and development. Here, we present a series of CTF-0 materials fabricated by two different approaches, a microwave-assisted synthesis and an ionothermal method, for water splitting driven by visible-light irradiation. The material (CTF-0-M2) synthesized by microwave technology shows a high photocatalytic activity for hydrogen evolution (up to 7010 µmol h-1 g-1), which is 7 times higher than another (CTF-0-I) prepared by conventional ionothermal trimerization under identical photocatalytic conditions. This leads to a high turnover number (TON) of 726 with respect to the platinum cocatalyst after seven cycles under visible light. We attribute this to the narrowed band gap, the most negative conduction band, and the rapid photogenerated charge separation and transfer. On the other hand, the material prepared by the ionothermal method is the most efficient one for oxygen evolution. CTF-0-I initially produces ca. 6 times greater volumes of oxygen gas than CTF-0-M2 under identical experimental conditions. CTF-0-I presents an apparent quantum efficiency (AQY) of 5.2% at 420 nm for oxygen production without any cocatalyst. The activity for water oxidation exceeds that of most reported CTFs due to a large driving force for oxidation and a large number of active sites. Our findings indicate that the band positions and the interlayer stacking structures of CTF-0 were modulated by varying synthesis conditions. These modulations impact the optical and redox properties, resulting in an enhanced performance for photocatalytic hydrogen and oxygen evolution, confirmed by first-principles calculations.

Effects of Loading Frequency and Loading Type on High-Cycle and Very-High-Cycle Fatigue of a High-Strength Steel.

High-cycle and very-high-cycle fatigue tests via rotary bending (52.5 Hz), electromagnetic resonance (120 Hz) axial cycling, and ultrasonic (20 kHz) axial cycling were performed for a high-strength steel with three heat treatment conditions, and the effects of loading frequency and loading type on fatigue strength and fatigue life were investigated. The results revealed that the loading frequency effect is caused by the combined response of strain rate increase and induced temperature rise. A parameter η was proposed to judge the occurrence of loading frequency effect, and the calculated results were in agreement with the experimental data. In addition, a statistical method based on the control volume was used to reconcile the effect of loading type, and the predicted data were consistent with the experimental results.

Mimicking Natural Photosynthesis: Solar to Renewable H2 Fuel Synthesis by Z-Scheme Water Splitting Systems.

Visible light-driven water splitting using cheap and robust photocatalysts is one of the most exciting ways to produce clean and renewable energy for future generations. Cutting edge research within the field focuses on so-called "Z-scheme" systems, which are inspired by the photosystem II-photosystem I (PSII/PSI) coupling from natural photosynthesis. A Z-scheme system comprises two photocatalysts and generates two sets of charge carriers, splitting water into its constituent parts, hydrogen and oxygen, at separate locations. This is not only more efficient than using a single photocatalyst, but practically it could also be safer. Researchers within the field are constantly aiming to bring systems toward industrial level efficiencies by maximizing light absorption of the materials, engineering more stable redox couples, and also searching for new hydrogen and oxygen evolution cocatalysts. This review provides an in-depth survey of relevant Z-schemes from past to present, with particular focus on mechanistic breakthroughs, and highlights current state of the art systems which are at the forefront of the field.

A Nanojunction Polymer Photoelectrode for Efficient Charge Transport and Separation.

A metal-free photoanode nanojunction architecture, composed of B-doped carbon nitride nanolayer and bulk carbon nitride, was fabricated by a one-step approach. This type of nanojunction (s-BCN) overcomes a few intrinsic drawbacks of carbon nitride film (severe bulk charge recombination and slow charge transfer). The top layer of the nanojunction has a depth of ca. 100 nm and the bottom layer is ca. 900 nm. The nanojunction photoanode results into a 10-fold higher photocurrent than bulk graphitic carbon nitride (G-CN) photoanode, with a record photocurrent density of 103.2 µA cm-2 at 1.23 V vs. RHE under one sun irradiation and an extremely high incident photon-to-current efficiency (IPCE) of ca. 10 % at 400 nm. Electrochemical impedance spectroscopy, Mott-Schottky plots, and intensity-modulated photocurrent spectroscopy show that such enhancement is mainly due to the mitigated deep trap states, a more than 10 times faster charge transfer rate and nearly three times higher conductivity due to the nanojunction architecture.