Enhanced Photobiocatalytic Cascades at Pickering Droplet Interfaces.

Developing new methods to engineer photobiocatalytic reactions is of utmost significance for artificial photosynthesis, but it remains a grand challenge due to the intrinsic incompatibility of biocatalysts with photocatalysts. In this work, photocatalysts and enzymes were spatially colocalized at Pickering droplet interfaces, where the reaction microenvironment and the spatial distance between two distinct catalysts were exquisitely regulated to achieve unprecedented photobiocatalytic cascade reactions. As proof of the concept, ultrathin graphitic carbon nitride nanosheets loaded with Au nanoparticles were precisely positioned in the outer interfacial layer of Pickering oil droplets to produce H2O2 under light irradiation, while enzymes were exactly placed in the inner interfacial layer to catalyze the subsequent biocatalytic oxidation reactions using in situ formed H2O2 as an oxidant. In the alkene epoxidation and thioether oxidation, our interfacial photobiocatalytic cascades showed a 2.0-5.8-fold higher overall reaction efficiency than the photobiocatalytic cascades in the bulk water phase. It was demonstrated that spatial localization of the photocatalyst and the enzyme at Pickering oil droplet interfaces not only provided their respective preferable reaction environments and intimate proximity for rapid H2O2 transport but also protected the enzyme from oxidative inactivation caused by the photogenerated species. These remarkable interfacial effects contributed to the significantly enhanced photobiocatalytic cascading efficiency. Our work presents an innovative photobiocatalytic reaction system with manifold benefits, providing a cutting-edge platform for solar-driven chemical transformations via photobiocatalysis.

Photocatalytic and Electrocatalytic Generation of Hydrogen Peroxide: Principles, Catalyst Design and Performance.

Hydrogen peroxide (H2O2) is a high-demand organic chemical reagent and has been widely used in various modern industrial applications. Currently, the prominent method for the preparation of H2O2 is the anthraquinone oxidation. Unfortunately, it is not conducive to economic and sustainable development since it is a complex process and involves unfriendly environment and potential hazards. In this context, numerous approaches have been developed to synthesize H2O2. Among them, photo/electro-catalytic ones are considered as two of the most promising manners for on-site synthesis of H2O2. These alternatives are sustainable in that only water or O2 is required. Namely, water oxidation (WOR) or oxygen reduction (ORR) reactions can be further coupled with clean and sustainable energy. For photo/electro-catalytic reactions for H2O2 generation, the design of the catalysts is extremely important and has been extensively conducted with an aim to obtain ultimate catalytic performance. This article overviews the basic principles of WOR and ORR, followed by the summary of recent progresses and achievements on the design and performance of various photo/electro-catalysts for H2O2 generation. The related mechanisms for these approaches are highlighted from theoretical and experimental aspects. Scientific challenges and opportunities of engineering photo/electro-catalysts for H2O2 generation are also outlined and discussed.

Catalytic ozonation of hard COD in coking wastewater with Fe2O3/Al2O3-SiC: From catalyst design to industrial application.

Development of robust, reactive, and inexpensive catalyst for pollutants abatement with catalytic ozonation is of great significance. Herein, the effect of a robust and easy-recovery catalyst, Fe2O3/Al2O3-SiC, for the catalytic ozonation of hardly biodegradable COD (hard COD) in coking wastewater had been explored. Al-O-Si bond formed on modified SiC through the substitution of hydrogen in surficial Si-OH groups by Al3+. The Lewis acid sites improved the adsorption of ozone and facilitated the formation of ·OH and O2·-. For coking wastewater treatment, the removal ratio of hard COD and the generation speed of hydroxyl radical (Rct) in the catalytic ozonation process were 71% and 253% higher than those in the ozonation group, respectively. Ozone utilization increased from 0.44 g COD removed/g O3 in the ozonation group to 1.42 g COD removed/g O3 in the Fe2O3/Al2O3-SiC catalytic ozonation group. In a full-scale application, Fe2O3/Al2O3-SiC catalytic ozonation decreased the consumption of O3 to 60 mg L-1 and decreased the operation cost by 50%. These results provided an approachable way for sharing the extraordinary capacity of ozone for contaminants remediation in industrial applications.

Multifunctional Hyphae Carbon Powering Lithium-Sulfur Batteries.

Biotechnology can bring new breakthroughs on design and fabrication of energy materials and devices. In this work, a novel and facile biological self-assembly technology to fabricate multifunctional Rhizopus hyphae carbon fiber (RHCF) and its derivatives on a large scale for electrochemical energy storage is proposed. Crosslinked hollow carbon fibers are successfully prepared by conversion of Rhizopus hyphae, and macroscopic production of centimeter-level carbon balls consisting of hollow RHCFs is further realized. Moreover, the self-assembled RHCF balls show strong adsorption characteristics on metal ions and can be converted into a series of derivatives such as RHCF/metal oxides. Notably, the designed RHCF derivatives are demonstrated with powerful multifunctionability as cathode, anode, and separator for lithium-sulfur batteries (LSBs). The RHCF can act as the host material to combine with metal oxide (CoO) and S, Li metal, and a polypropylene (PP) separator to form a new RHCF/CoO-S cathode, an RHCF/Li anode, and an RHCF/PP separator, respectively. Consequently, the optimized LSB full cell presents excellent cycling performance and superior high-rate capacity (881.3 mA h g-1 at 1 C). This work provides a new method for large-scale preparation of hollow carbon fibers and derivatives for advanced energy storage and conversion.

A Powerful One-Step Puffing Carbonization Method for Construction of Versatile Carbon Composites with High-Efficiency Energy Storage.

Carbon materials play a critical role in the advancement of electrochemical energy storage and conversion. Currently, it is still a great challenge to fabricate versatile carbon-based composites with controlled morphology, adjustable dimension, and tunable composition by a one-step synthesis process. In this work, a powerful one-step maltose-based puffing carbonization technology is reported to construct multiscale carbon-based composites on large scale. A quantity of composite examples (e.g., carbon/metal oxides, carbon/metal nitrides, carbon/metal carbides, carbon/metal sulfides, carbon/metals, metal/semiconductors, carbon/carbons) are prepared and demonstrated with required properties. These well-designed composites show advantages of large porosity, hierarchical porous structure, high conductivity, tunable components, and proportion. The formation mechanism of versatile carbon composites is attributed to the puffing-carbonization of maltose plus in situ carbothermal reaction between maltose and precursors. As a representative example, Li2 S is in situ implanted into a hierarchical porous cross-linked puffed carbon (CPC) matrix to verify its application in lithium-sulfur batteries. The designed S-doped CPC/Li2 S cathode shows superior electrochemical performance with higher rate capacity (621 mAh g-1 at 2 C), smaller polarization and enhanced long-term cycles as compared to other counterparts. The research provides a general way for the construction of multifunctional component-adjustable carbon composites for advanced energy storage and conversion.

Mesoporous RhRu Nanosponges with Enhanced Water Dissociation toward Efficient Alkaline Hydrogen Evolution.

Lowering the energy barrier of water dissociation is critical to achieving highly efficient hydrogen evolution in alkaline conditions. Herein, we reported mesoporous RhRu nanosponges with enhanced water dissociation behavior as a new class of high-performance electrocatalysts for alkaline hydrogen evolution reaction (HER). The obtained nanosponges have a binary alloy structure (fcc) and a highly porous structure with high surface area. Our RhRu catalyst displayed an outstanding HER activity with an overpotential of 25 mV at 10 mA cm-2 and a Tafel slope of 47.5 mV dec-1 in 1.0 M KOH, which significantly outperformed that of commercial Pt/C catalyst and was even comparable to the classic Pt/metal (hydro)oxide catalysts. Density functional theory (DFT) calculations disclosed that charge redistribution on the RhRu alloy surface enabled tuning of the Ru d-band center and then promoted the adsorption and dissociation of water molecules. Based on the experimental results and theoretical modeling, a bifunctional mechanism contributed to the remarkable alkaline HER activity on the RhRu catalyst surface.

A Phosphorus-Doped Ag@Pd Catalyst for Enhanced CC Bond Cleavage during Ethanol Electrooxidation.

Ethanol is preferred to be oxidized into CO2 for the construction of a high-performance direct ethanol fuel cell since this complete ethanol oxidation reaction (EOR) transfers 12 electrons. However, this EOR is sluggish and has the low activity as well as poor selectivity. To promote such a favorable EOR, more exactly the cleavage selectivity of CC bonds in ethanol, phosphorus-doped silver-core-and-Pd-shell catalysts (denoted as Ag@PdP) are designed and synthesized. In the alkaline media, a Ag@Pd2 P0.2 catalyst is superior toward EOR into CO2 . It exhibits seven times higher mass activity and six times higher selectivity than the benchmark Pd/C catalyst. As confirmed by means of density functional theory calculation and in situ Fourier-transform infrared spectroscopy, such high performance stems from an increased adsorption energy of OH radicals on the Pd active sites. Meanwhile, the tensile strain effect of a core-shell structure of this Ag@Pd2 P0.2 catalyst favors the formation of adsorbed CH3 CO intermediate, the key species for the enhanced C-C cleavage into CO2 , instead of acetate. The proposed way to design and synthesize such high-performance EOR catalysts will explore the practical applications of direct alkaline ethanol fuel cells.

Anchoring SnS2 on TiC/C Backbone to Promote Sodium Ion Storage by Phosphate Ion Doping.

Tin disulfide (SnS2 ) shows promising properties toward sodium ion storage with high capacity, but its cycle life and high rate capability are still undermined as a result of poor reaction kinetics and unstable structure. In this work, phosphate ion (PO4 3- )-doped SnS2 (P-SnS2 ) nanoflake arrays on conductive TiC/C backbone are reported to form high-quality P-SnS2 @TiC/C arrays via a hydrothermal-chemical vapor deposition method. By virtue of the synergistic effect between PO4 3- doping and conductive network of TiC/C arrays, enhanced electronic conductivity and enlarged interlayer spacing are realized in the designed P-SnS2 @TiC/C arrays. Moreover, the introduced PO4 3- can result in favorable intercalation/deintercalation of Na+ and accelerate electrochemical reaction kinetics. Notably, lower bandgap and enhanced electronic conductivity owing to the introduction of PO4 3- are demonstrated by density function theory calculations and UV-visible absorption spectra. In view of these positive factors above, the P-SnS2 @TiC/C electrode delivers a high capacity of 1293.5 mAh g-1 at 0.1 A g-1 and exhibits good rate capability (476.7 mAh g-1 at 5 A g-1 ), much better than the SnS2 @TiC/C counterpart. This work may trigger new enthusiasm on construction of advanced metal sulfide electrodes for application in rechargeable alkali ion batteries.

Design of 3D Hollow Porous Heterogeneous Nickel-Cobalt Phosphides for Synergistically Enhancing Catalytic Performance for Electrooxidation of Methanol.

The synergistic effect among different components and the structural and morphological control of catalytic nanomaterials have attracted considerable research interest in the field of electrocatalysis, as using a rational design of the catalytic nanomaterials with the desired structure, morphology, and chemical compositions is an effective strategy for enhancing catalytic performance. Here, by changing the Ni/Co atomic ratio of raw materials, a series of samples with a three-dimensional (3D) hollow porous ternary multicomponent heterostructure has been successfully synthesized via a facile template-free solvothermal approach and subsequently annealing and phosphating treatments, and its formation mechanism is also investigated. By virtue of compositional and structural advantages, the optimized Ni1Co2Px (NiCoP/CoP/CoP2) nanoparticles show very high mass activity (436.9 mA mg-1) and area-specific activity (155 mA cm-2), as well as remarkable durability toward the methanol electrooxidation reaction (MOR) in alkaline solution. This catalytic activity is better than those of most of reported Ni/Co-based nonprecious metal catalysts. Particularly, a multicomponent synergistic effect on the MOR was observed. The present study not only provides a simple method for the fabrication of 3D hollow porous multicomponent composite nanomaterials, but also gives insights into the synergistic effect among the porous structure, chemical compositions, and catalytic activity of nanomaterials in the electrocatalytic oxidation of methanol.

Pore structure dependent activity and durability of mesoporous rhodium nanoparticles towards the methanol oxidation reaction.

This work reports a significant effect of porous structures on the electrocatalytic methanol oxidation performances of Rh-based catalysts. It is demonstrated that a three-dimensional net-like mesoporous structure with ultrathin subunits is beneficial to exposing more active sites and boosting electron transfer inside particles, thus presenting the highest activity.

Epitaxial Cubic Silicon Carbide Photocathodes for Visible-Light-Driven Water Splitting.

Cubic silicon carbide (3C-SiC) material feature a suitable bandgap and high resistance to photocorrosion. Thus, it has been emerged as a promising semiconductor for hydrogen evolution. Here, the relationship between the photoelectrochemical properties and the microstructures of different SiC materials is demonstrated. For visible-light-derived water splitting to hydrogen production, nanocrystalline, microcrystalline and epitaxial (001) 3C-SiC films are applied as the photocathodes. The epitaxial 3C-SiC film presents the highest photoelectrochemical activity for hydrogen evolution, because of its perfect (001) orientation, high phase purity, low resistance, and negative conduction band energy level. This finding offers a strategy to design SiC-based photocathodes with superior photoelectrochemical performances.

Atomic Carbon Layers Supported Pt Nanoparticles for Minimized CO Poisoning and Maximized Methanol Oxidation.

Maximizing activity of Pt catalysts toward methanol oxidation reaction (MOR) together with minimized poisoning of adsorbed CO during MOR still remains a big challenge. In the present work, uniform and well-distributed Pt nanoparticles (NPs) grown on an atomic carbon layer, that is in situ formed by means of dry-etching of silicon carbide nanoparticles (SiC NPs) with CCl4 gas, are explored as potential catalysts for MOR. Significantly, as-synthesized catalysts exhibit remarkably higher MOR catalytic activity (e.g., 647.63 mA mg-1 at a peak potential of 0.85 V vs RHE) and much improved anti-CO poisoning ability than the commercial Pt/C catalysts, Pt/carbon nanotubes, and Pt/graphene catalysts. Moreover, the amount of expensive Pt is a few times lower than that of the commercial and reported catalyst systems. As confirmed from density functional theory (DFT) calculations and X-ray absorption fine structure (XAFS) measurements, such high performance is due to reduced adsorption energy of CO on the Pt NPs and an increased amount of adsorbed energy OH species that remove adsorbed CO fast and efficiently. Therefore, these catalysts can be utilized for the development of large-scale and industry-orientated direct methanol fuel cells.

Particle size-control enables extraordinary activity of ruthenium nanoparticles/multiwalled carbon nanotube catalysts towards the oxygen reduction reaction.

Catalysts with high efficiency for the oxygen reduction reaction (ORR) play a vital important role in fuel cells and metal-air batteries. Herein, Ru nanoparticles are highly dispersed on functional multi-walled carbon nanotubes (MWCNTs) by a facile impregnation-reduction method. The particle sizes of Ru nanoparticles are simply and effectively adjusted by the concentration of the Ru precursor. Benefiting from the optimal Ru particle size (2.1 nm), a large electrochemically active surface area and fast electron transport, the Ru/MWCNT catalyst shows outstanding ORR activity and durability via a four-electron pathway, producing a diffusion-limited current density of 4.7 mA cm-2 with a half-wave potential of 0.72 V (vs. RHE). Such performance is better than that of a commercial 10 wt% Pt/C catalyst. Density functional theory calculation results reveal that the Oads adsorption on the surface of Ru increases gradually with the addition of the RuOx layer. The Ru/MWCNT catalyst with a particle size of 2.1 nm features appropriate Oads adsorption energy due to the formation of an optimal RuOx/Ru interface for the facilitation of the ORR.

Synergistic Effect of Segregated Pd and Au Nanoparticles on Semiconducting SiC for Efficient Photocatalytic Hydrogenation of Nitroarenes.

Efficient catalytic hydrogenation of nitroarenes to anilines with molecular hydrogen at room temperature is still a challenge. In this study, this transformation was achieved by using a photocatalyst of SiC-supported segregated Pd and Au nanoparticles. Under visible-light irradiation, the nitrobenzene hydrogenation reached a turnover frequency as high as 1715 h-1 at 25 °C and 0.1 MPa of H2 pressure. This exceptional catalytic activity is attributed to a synergistic effect of Pd and Au nanoparticles on the semiconducting SiC, which is different from the known electronic or ensemble effects in Pd-Au catalysts. This kind of synergism originates from the plasmonic electron injection of Au and the Mott-Schottky contact at the interface between Pd and SiC. This three-component system changes the electronic structures of the SiC surface and produces more active sites to accommodate the active hydrogen that spills over from the surface of Pd. These active hydrogen species have weaker interactions with the SiC surface and thus are more mobile than on an inert support, resulting in an ease in reacting with the N═O bonds in nitrobenzene absorbed on SiC to produce aniline.

Porous TiO2 Nanotubes with Spatially Separated Platinum and CoOx Cocatalysts Produced by Atomic Layer Deposition for Photocatalytic Hydrogen Production.

Efficient separation of photogenerated electrons and holes, and associated surface reactions, is a crucial aspect of efficient semiconductor photocatalytic systems employed for photocatalytic hydrogen production. A new CoOx /TiO2 /Pt photocatalyst produced by template-assisted atomic layer deposition is reported for photocatalytic hydrogen production on Pt and CoOx dual cocatalysts. Pt nanoclusters acting as electron collectors and active sites for the reduction reaction are deposited on the inner surface of porous TiO2 nanotubes, while CoOx nanoclusters acting as hole collectors and active sites for oxidation reaction are deposited on the outer surface of porous TiO2 nanotubes. A CoOx /TiO2 /Pt photocatalyst, comprising ultra-low concentrations of noble Pt (0.046 wt %) and CoOx (0.019 wt %) deposited simultaneously with one atomic layer deposition cycle, achieves remarkably high photocatalytic efficiency (275.9 µmol h-1 ), which is nearly five times as high as that of pristine TiO2 nanotubes (56.5 µmol h-1 ). The highly dispersed Pt and CoOx nanoclusters, porous structure of TiO2 nanotubes with large specific surface area, and the synergetic effect of the spatially separated Pt and CoOx dual cocatalysts contribute to the excellent photocatalytic activity.

Mesoporous NiCo2O4 Nanoplates on Three-Dimensional Graphene Foam as an Efficient Electrocatalyst for the Oxygen Reduction Reaction.

Catalysts for the oxygen reduction reaction (ORR) are highly important in fuel cells and metal-air batteries. Cheap ORR catalysts with ultrahigh electrochemical activity, selectivity, and stability are extremely desirable but still remain challenging. Herein, mesoporous NiCo2O4 nanoplate (NP) arrays on three-dimensional (3D) graphene foam are shown to be a highly economical ORR catalyst. This mesoporous mixed-valence oxide can provide more electrocatalytic active sites with increased accessible surface area. In addition, graphene-foam-supported NiCo2O4 NP arrays have a 3D hierarchical porous structure, which is of great benefit to ion diffusion and electron transfer. As a result, the mesoporous NiCo2O4 NP arrays/graphene foam catalyst exhibits outstanding ORR performance with the four-electron reduction of O2 to H2O in alkaline media. Furthermore, the mesoporous catalyst shows enhanced electrocatalytic activity with a half-wave potential of 0.86 V vs RHE and better stability compared with a commercial Pt/C catalyst.

NiO/SiC nanocomposite prepared by atomic layer deposition used as a novel electrocatalyst for nonenzymatic glucose sensing.

NiO nanoparticles are deposited onto SiC particles by atomic layer deposition (ALD). The structure of the NiO/SiC hybrid material is investigated by inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The size of the NiO nanoparticles is flexible and can be adjusted by altering the cycle number of the NiO ALD. Electrochemical measurements illustrate that NiO/SiC prepared with 600 cycles for NiO ALD exhibits the highest glucose sensing ability in alkaline electrolytes with a low detection limit of 0.32 µM (S/N = 3), high sensitivity of 2.037 mA mM(-1) cm(-2), a linear detection range from approximately 4 µM to 7.5 mM, and good stability. Its sensitivity is about 6 times of that for commercial NiO nanoparticles and NiO/SiC nanocomposites prepared by a traditional incipient wetness impregnation method. It is revealed that the superior electrochemical ability of ALD NiO/SiC is ascribed to the strong interaction between NiO and the SiC substrate and the high dispersity of NiO nanoparticles on the SiC surface. These results suggest that ALD is an effective way to deposit NiO on SiC for nonenzymatic glucose sensing.

Enhanced photoelectrochemical water splitting performance of TiO2 nanotube arrays coated with an ultrathin nitrogen-doped carbon film by molecular layer deposition.

Vertically oriented TiO2 nanotube arrays (TNTAs) were conformally coated with an ultrathin nitrogen-doped (N-doped) carbon film via the carbonization of a polyimide film deposited by molecular layer deposition and simultaneously hydrogenated, thereby creating a core/shell nanostructure with a precisely controllable shell thickness. The core/shell nanostructure provides a larger heterojunction interface to substantially reduce the recombination of photogenerated electron-hole pairs, and hydrogenation enhances solar absorption of TNTAs. In addition, the N-doped carbon film coating acts as a high catalytic active surface for oxygen evolution reaction, as well as a protective film to prevent hydrogen-treated TiO2 nanotube oxidation by electrolyte or air. As a result, the N-doped carbon film coated TNTAs displayed remarkably improved photocurrent and photostability. The TNTAs with a N-doped carbon film of ∼ 1 nm produces a current density of 3.6 mA cm(-2) at 0 V vs. Ag/AgCl under the illumination of AM 1.5 G (100 mW cm(-2)), which represents one of the highest values achieved with modified TNTAs. Therefore, we propose that ultrathin N-doped carbon film coating on materials is a viable approach to enhance their PEC water splitting performance.

In situ grafted carbon on sawtooth-like SiC supported Ni for high-performance supercapacitor electrodes.

A novel C-Ni-SiC composite using sawtooth-like SiC as support and carbon as modified material was prepared by hydrothermal synthesis and thermochemical pyrolysis. As a supercapacitor electrode, it exhibits very high specific capacitance (1780 F g(-1)) and excellent cycling performance (>96% for 2500 cycles).

Large scale production of highly-qualified graphene by ultrasonic exfoliation of expanded graphite under the promotion of (NH4)2CO3 decomposition.

Highly-qualified graphene was prepared by the ultrasonic exfoliation of commercial expanded graphite (EG) under the promotion of (NH4)2CO3 decomposition. The yield of graphene from the first exfoliation is 7 wt%, and it can be increased to more than 65 wt% by repeated exfoliations. Atomic force microscopy, x-ray photoelectron spectroscopy and Raman analysis show that the as-prepared graphene only has a few defects or oxides, and more than 95% of the graphene flakes have a thickness of ~1 nm. The electrochemical performance of the as-prepared graphene is comparable to reduced graphene oxide in the determination of dopamine (DA) from the mixed solution of ascorbic acid, uric acid and DA. These results show that the decomposition of (NH4)2CO3 molecules in the EG layers under ultrasonication promotes the exfoliation of graphite and provides a low-priced route for large scale production of highly-quality graphene.