Multiple reaction pathway on alkaline earth imide supported catalysts for efficient ammonia synthesis.

The tunability of reaction pathways is required for exploring efficient and low cost catalysts for ammonia synthesis. There is an obstacle by the limitations arising from scaling relation for this purpose. Here, we demonstrate that the alkali earth imides (AeNH) combined with transition metal (TM = Fe, Co and Ni) catalysts can overcome this difficulty by utilizing functionalities arising from concerted role of active defects on the support surface and loaded transition metals. These catalysts enable ammonia production through multiple reaction pathways. The reaction rate of Co/SrNH is as high as 1686.7 mmol·gCo-1·h-1 and the TOFs reaches above 500 h-1 at 400 °C and 0.9 MPa, outperforming other reported Co-based catalysts as well as the benchmark Cs-Ru/MgO catalyst and industrial wüstite-based Fe catalyst under the same reaction conditions. Experimental and theoretical results show that the synergistic effect of nitrogen affinity of 3d TMs and in-situ formed NH2- vacancy of alkali earth imides regulate the reaction pathways of the ammonia production, resulting in distinct catalytic performance different from 3d TMs. It was thus demonstrated that the appropriate combination of metal and support is essential for controlling the reaction pathway and realizing highly active and low cost catalysts for ammonia synthesis.

Tailoring the growth route of lithium peroxide through the rational design of a sodium-doped nickel phosphate catalyst for lithium-oxygen batteries.

Tailoring the morphology and structure of Li2O2, the discharge product of lithium-oxygen batteries (LOBs), through the rational design of cathode catalysts is an efficient strategy to promote the electrochemical performance of LOBs. In this work, sodium-doped nickel phosphate nanorods (Na-NiPO NRs) grown on Ni foam (NF) were prepared by the hydrothermal method and subsequent calcination. For the Na-NiPO NRs, the electronic structure could be optimized and abundant void space among the nanorods would provide abundant transport channels. Adopted as the cathodes, the Na-NiPO NRs could facilitate the uniform growth of sea cucumber-like Li2O2 with sufficient Li2O2-electrolyte and Li2O2-catalyst interfaces, significantly promoting the charge process. Therefore, LOBs could deliver a high discharge capacity of 10365.0 mA h g-1 at 100 mA g-1. And a low potential gap of 1.16 V can be achieved at 200 mA g-1 with a capacity of 500 mA h g-1. The proposed strategy demonstrates the role of the morphology and electronic structure of the cathode catalysts in tuning the Li2O2 morphology and provides a novel approach for achieving high-performance LOBs.

Poly(p-phenylenediamine)-Coated Metal-Organic Frameworks for High-Performance Sodium-Ion Batteries: The Balance of Capacity and Stability.

Metal-organic frameworks (MOFs) with well-defined porous structures and highly active frameworks are considered as promising electrode materials for sodium-ion batteries (SIBs). However, the structure pulverization upon sodiation/desodiation impacts on their practical application in SIBs. To address this issue, poly(p-phenylenediamine) (PPA) was uniformly coated onto the surface of MIL-88A, a typical Fe-based MOF through in situ polymerization initiated by the metal ions (Fe3+) of MIL-88A. Used as an anode material for SIBs, the PPA-coated MIL-88A, denoted as PPA@MIL-88A, showed significantly improved electrochemical performance. A reversible capacity as high as 230 mAh g-1 was achieved at 0.2 A g-1 even after 500 cycles. MIL-88A constructed with electrochemically active Fe3+ and fumaric acid ligands guarantees the high specific capacity, while the PPA polymer coating effectively inhibits the pulverization of MIL-88A. This work provides an efficient strategy for improving the structure and cycling stability of MOFs-based electrode materials.

Tailoring the Growth and Morphology of Lithium Peroxide: Nickel Sulfide/Nickel Phosphate Nanotubes with Optimized Electronic Structure for Lithium-Oxygen Batteries.

Heterogeneous crystalline-amorphous structures, with tunable electronic structures and morphology, hold immense promise as catalysts for lithium-oxygen batteries (LOBs). Herein, a nanotube network constructed by crystalline nickel sulfide/amorphous nickel phosphate (NiS/NiPO) heterostructure is prepared on Ni foam through the sulfurization of the precursor generated hydrothermally. Used as cathodes, the NiS/NiPO nanotubes with optimized electronic structure can induce the deposition of the highly porous and interconnected structure of Li2 O2 with rich Li2 O2 -electrolyte interfaces. Abundant active sites can be created on NiS/NiPO through the charge redistribution for the uniform nucleation and growth of Li2 O2 . Moreover, nanotube networks endow cathodes with efficient transport channels and sufficient space for the accommodation of Li2 O2 . A high discharge capacity of 27 003.6 mAh g-1 and a low charge overpotential of 0.58 V at 1000 mAh g-1 can be achieved at 200 mA g-1 . This work provides valuable insight into the unique role of the electronic structure and morphology of catalysts in the formation mechanisms of Li2 O2 and the performances of LOBs.

Design of the Synergistic Rectifying Interfaces in Mott-Schottky Catalysts.

The functions of interfacial synergy in heterojunction catalysts are diverse and powerful, providing a route to solve many difficulties in energy conversion and organic synthesis. Among heterojunction-based catalysts, the Mott-Schottky catalysts composed of a metal-semiconductor heterojunction with predictable and designable interfacial synergy are rising stars of next-generation catalysts. We review the concept of Mott-Schottky catalysts and discuss their applications in various realms of catalysis. In particular, the design of a Mott-Schottky catalyst provides a feasible strategy to boost energy conversion and chemical synthesis processes, even allowing realization of novel catalytic functions such as enhanced redox activity, Lewis acid-base pairs, and electron donor-acceptor couples for dealing with the current problems in catalysis for energy conversion and storage. This review focuses on the synthesis, assembly, and characterization of Schottky heterojunctions for photocatalysis, electrocatalysis, and organic synthesis. The proposed design principles, including the importance of constructing stable and clean interfaces, tuning work function differences, and preparing exposable interfacial structures for designing electronic interfaces, will provide a reference for the development of all heterojunction-type catalysts, electrodes, energy conversion/storage devices, and even super absorbers, which are currently topics of interest in fields such as electrocatalysis, fuel cells, CO2 reduction, and wastewater treatment.

High-Performance PEO-Based All-Solid-State Battery Achieved by Li-Conducting High Entropy Oxides.

A rock-salt-structured Li-conducting high entropy oxide was prepared and utilized as an active filler in a polyethylene oxide (PEO)-based solid-state composite electrolyte. X-ray diffraction and high-resolution transmission electron microscopy were adopted to analyze the crystal structure of the high entropy oxide containing 20% of Li ions (HL20). The HL20 was crystallized in the Fm3̅m space group with Li+ ions located at the center of the MO6 octahedra. The ionic conductivity of the composite membrane at 30 °C reaches 3.44 × 10-5 S cm-1. The inflection point of activation energy of the membrane with HL20 decreases by 5 °C compared with that of the pure PEO membrane. In the galvanostatic plating/stripping test, the Li||Li symmetric batteries could be cycled at a current density of 200 µA cm-2 for over 1200 h with an overpotential of 140 mV. The Li||LiFePO4 full battery could be charged/discharged at 0.5 C for 100 circles with a high capacity retention rate of 91%. Excellent rate performance is also achieved at lower temperatures and higher rates, showing the superiority of HL20 as an active filler. This work sheds light on the development of high entropy oxide as a new type of fast ionic conductor, promoting the practical application of all-solid-state batteries at a lower temperature.

Direct Oxygen Transfer from H2 O to Cyclooctene over Electron-Rich RuO2 Nanocrystals for Epoxidation and Hydrogen Evolution.

Production of more than 20 million tons of epoxides per year from olefins suffers from low atom economy due to the use of oxidants and complex catalysts with unsatisfactory selectivity, leading to huge environmental and economic costs. We present a proof-of-concept application of electron-rich RuO2 nanocrystals to boost the highly selective epoxidation of cyclooctene via direct oxygen transfer from water as the sole oxygen source under mild conditions. The enhanced electron enrichment of RuO2 nanocrystals via the Schottky effect with nitrogen-doped carbons largely promotes the capture and activation of cyclooctene to give a high turnover frequency (260 h-1 ) of cyclooctene oxide, far surpassing the reported values (<20 h-1 ) of benchmarked catalysts at room temperature with oxidants. Our electron-rich RuO2 electrocatalysts enable efficient and durable hydrogen production (Faradaic efficiency >90 %) on the cathode without impacting on the selectivity to epoxide (>99 %) on the anode.

Novel design of cryptosystems for video/audio streaming via dynamic synchronized chaos-based random keys.

In this paper, a novel chaos-based cryptosystem is proposed to ensure the communication security of video/audio streaming in the network environment. Firstly, by the proposed synchronization controller for the master and slave chaotic systems, respectively, embedded in the transmitter and receiver, the cryptosystem can generate the synchronized and dynamic chaotic random numbers at the transmitter and receiver simultaneously. Then integrating the chaotic random numbers with SHA3-256 (Secure hash algorithm 3), the design of synchronized dynamic key generators (SDKGs) is completed. Continuously, we can apply the SDKGs to encrypt/decrypt streaming audio/video data. In our design, we introduce the AES CFB (Advanced encryption standard cipher feedback) encryption algorithm with SDKGs to encrypt the video/audio streaming. Then the cipher-text is transmitted to the receiver via the network public channel and it can be fully decrypted with the dynamic random keys synchronously generated at the receiver. A duplex audio/video cryptosystem is realized to illustrate the performance and feasibility of this proposed research. Finally, many tests and comparisons are performed to stress the quality of random sequences generated by proposed SDKGs.

Highly Reversible Zinc Anode Enabled by a Cation-Exchange Coating with Zn-Ion Selective Channels.

Rechargeable aqueous zinc-ion batteries (ZIBs) have attracted extensive attention due to their low cost and high safety. However, the critical issues of dendrite growth and side reactions on the Zn metal anode hinder the commercialization of ZIBs. Herein, we demonstrated that the formation of Zn4SO4(OH)6·5H2O byproducts is closely relevant to the direct contact between the Zn electrode and SO42-/H2O. On the basis of this finding, we developed a cation-exchange membrane of perfluorosulfonic acid (PFSA) coated on the Zn surface to regulate the Zn plating/stripping behavior. Importantly, the PFSA film with abundant sulfonic acid groups could simultaneously block the access of SO42- and H2O, accelerate the Zn2+ ion transport kinetics, and uniformize the electrical and Zn2+ ion concentration field on the Zn surface, thus achieving a highly reversible Zn plating/stripping process with corrosion-free and dendrite-free behavior. Consequently, the PFSA-modified Zn anode exhibits high reversibility with 99.5% Coulombic efficiency and excellent plating/stripping stability (over 1500 h), subsequently enabling a highly rechargeable Zn-MnO2 full cell. The strategy of the cation-exchange membrane proposed in this work provides a simple but efficient method for suppression of side reactions.

Facilitating Hot Electron Injection from Graphene to Semiconductor by Rectifying Contact for Vis-NIR-Driven H2 O2 Production.

Solar-driven production of hydrogen peroxide (H2 O2 ), as an important industrial chemical oxidant with an extensive range of applications, from oxygen reduction is a sustainable alternative to mainstream anthraquinone oxidation and direct hydrogenation of dioxygen methods. The efficiency of solar to hydrogen peroxide over semiconductor-based photocatalysts is still largely limited by the narrow light absorption to visible light. Here, the authors proposed and demonstrate the proof-of-concept application of light-generated hot electrons in a graphene/semiconductor (exemplified with widely used TiO2 ) dyad to largely extend visible light spectra up to 800 nm for efficient H2 O2 production. The well-designed graphene/semiconductor heterojunction has a rectifying interface with a zero barrier for the hot electron injection, largely boosting excited hot electrons with an average lifetime of ≈0.5 ps into charge carriers with a long fluorescent lifetime (4.0 ns) for subsequent H2 O2 production. The optimized dyadic photocatalyst can provide an H2 O2 yield of 0.67 mm g-1  h-1 under visible light irradiation (λ ≥ 400 nm), which is 20 times of the state-of-the-art noble-metal-free titanium oxide-based photocatalyst, and even achieves an H2 O2 yield of 0.14 mm g-1  h-1 upon photoexcitation by near-infrared-region light (≈800 nm).

Boosting Mass Exchange between Pd/NC and MoC/NC Dual Junctions via Electron Exchange for Cascade CO2 Fixation.

Merging existing catalysts together as a cascade catalyst may achieve "one-pot" synthesis of complex but functional molecules by simplifying multistep reactions, which is the blueprint of sustainable chemistry with low pollutant emission and consumption of energy and materials only when the smooth mass exchange between different catalysts is ensured. Effective strategies to facilitate the mass exchange between different active centers, which may dominate the final activity of various cascade catalysts, have not been reached until now, even though charged interfaces due to work function driven electron exchange have been widely observed. Here, we successfully constructed mass (reactants and intermediates) exchange paths between Pd/N-doped carbon and MoC/N-doped carbon induced by interfacial electron exchange to trigger the mild and cascade methylation of amines using CO2 and H2. Theoretical and experimental results have demonstrated that the mass exchange between electron-rich MoC and electron-deficient Pd could prominently improve the production of N,N-dimethyl tertiary amine, which results in a remarkably high turnover frequency value under mild conditions, outperforming the state-of-the-art catalysts in the literature by a factor of 5.9.

Toward Hydrogen-Free and Dendrite-Free Aqueous Zinc Batteries: Formation of Zincophilic Protective Layer on Zn Anodes.

Rechargeable aqueous Zn-ion batteries (ZIBs) are regarded as one of the most promising devices for the next-generation energy storage system. However, the uncontrolled dendrite growth on Zn metal anodes and the side hydrogen evolution reaction, which has not yet been well considered, hinder the practical application of these batteries. Herein, a uniform and robust metallic Sb protective layer is designed based on the theoretic calculation and decorated on Zn plate via in situ replacement reaction. Compared with the bare Zn plate, the as-prepared Zn@Sb electrode provides abundant zincophilic sites for Zn nucleation, and homogenizes the electric field around the Zn anode surface, both of which promote the uniform Zn deposition to achieve a dendrite-free morphology. Moreover, the Gibbs free energy (∆GH ) calculation and in situ characterization demonstrate that hydrogen evolution reaction can be effectively suppressed by the Sb layer. Consequently, Sb-modified Zn anodes exhibit an ultralow voltage hysteresis of 34 mV and achieve excellent cycling stability over 1000 h with hydrogen- and dendrite-free behaviors. This work provides a facile and effective strategy to suppress both hydrogen evolution reaction and dendrite growth.

Light-driven Oxidative Demethylation Reaction Catalyzed by a Rieske-type Non-heme Iron Enzyme Stc2.

Rieske-type non-heme iron oxygenases/oxidases catalyze a wide range of transformations. Their applications in bioremediation or biocatalysis face two key barriers: the need of expensive NAD(P)H as a reductant and a proper reductase to mediate the electron transfer from NAD(P)H to the oxygenases. To bypass the need of both the reductase and NAD(P)H, using Rieske-type oxygenase (Stc2) catalyzed oxidative demethylation as the model system, we report Stc2 photocatalysis using eosin Y/sulfite as the photosensitizer/sacrificial reagent pair. In a flow-chemistry setting to separate the photo-reduction half-reaction and oxidation half-reaction, Stc2 photo-biocatalysis outperforms the Stc2-NAD(P)H-reductase (GbcB) system. In addition, in a few other selected Rieske enzymes (NdmA, CntA, and GbcA), and a flavin-dependent enzyme (iodotyrosine deiodinase, IYD), the eosin Y/sodium sulfite photo-reduction pair could also serve as the NAD(P)H-reductase surrogate to support catalysis, which implies the potential applicability of this photo-reduction system to other redox enzymes.

Heteroatom-Embedded Approach to Vinylene-Linked Covalent Organic Frameworks with Isoelectronic Structures for Photoredox Catalysis.

Embedding heteroatoms into the main backbones of polymeric materials has become an efficient tool for tailoring their structures and improving their properties. However, owing to comparatively harsh heteroatom-doping conditions, this has rarely been explored in covalent organic frameworks (COFs). Herein, upon aldol condensation of a trimethyl-substituted pyrylium salt with a tritopic aromatic aldehyde, a two-dimensional oxonium-embedded COF with vinylene linkages was achieved, which was further converted to a neutral pyridine-cored COF by in situ replacement of oxonium ions with nitrogen atoms under ammonia treatment. The two heteroatom-embedded COFs are conceptually isoelectronic with each other, featuring similar geometric structures but different electronic structures, rendering them capable of catalyzing the visible-light-promoted multi-component synthesis of tri-substituted pyridine derivatives with good recyclability.

Construction of Large Non-Localized π-Electron System for Enhanced Sodium-Ion Storage.

Organic electrode materials with the advantages of renewability, environment-friendliness, low cost, and high capacity have received widespread attention in recent years for sodium-ion batteries. However, small molecular organic materials suffer from issues such as low conductivity and the high dissolution rate in electrolytes. Herein, a phthalocyanine derivative (TPcDS) with a large non-localized π-electron system, obtained through thermodynamic polymerization of 4-aminophthalonitrile (AP) monomers, is designed to address these issues. According to the density function theory calculation, six sodium ions can be attracted by one polymer molecule, indicating a high theoretical capacity of 375 mA h g-1 . The TPcDS molecule realizes sodium storage through a non-localized π-electron system of phthalocyanine macrocycles. When employed as an anode material for sodium-ion batteries, the functional groups of phthalocyanine macrocycles, such as CN groups in TPcDS, experience obviously reversible structural variation upon discharge/charge. A high reversible capacity of 364 mAh g-1 is achieved at a current density of 0.05 A g-1 , and a charge capacity of as high as 246 mAh g-1 is still maintained after 500 cycles at 0.1 A g-1 . This work provides an effective strategy for the design and synthesis of new oligomeric organic electrode materials.

Tunable Surface Electric Field of Electrocatalysts via Constructing Schottky Heterojunctions for Selective Conversion of Trash Ions to Treasures.

Surface electric field of catalyst is widely recognized as one of the key points to boost catalytic activity. However, there is still a lack of convenient ways to tune the surface electric field to selectively boost the catalytic conversions of different types of reactants in specific catalytic reactions. Here, we introduce a conceptually new method to tune the surface electric field of electrode materials by adjusting the number and density of heterojunctions inside. Both theoretical and experimental results prove that the well-designed surface electric field of an electrocatalyst plays a key role in facilitating pre-adsorption and/or activation of reactants for selective conversion of trash ions to useful products in hydrogen and oxygen evolution reactions as well as NOx - reduction reactions.

Heterojunction-Based Electron Donators to Stabilize and Activate Ultrafine Pt Nanoparticles for Efficient Hydrogen Atom Dissociation and Gas Evolution.

Platinum (Pt) is the most effective bench-marked catalyst for producing renewable and clean hydrogen energy by electrochemical water splitting. There is demand for high HER catalytic activity to achieve efficient utilization and minimize the loading of Pt in catalysts. In this work, we significantly boost the HER mass activity of Pt nanoparticles in Ptx /Co to 8.3 times higher than that of commercial Pt/C by using Co/NC heterojunctions as a heterogeneous version of electron donors. The highly coupled interfaces between Co/NC and Pt metal enrich the electron density of Pt nanoparticles to facilitate the adsorption of H+ , the dissociation of Pt-H bonds and H2 release, giving the lowest HER overpotential of 6.9 mV vs. RHE at 10 mA cm-2 in acid among reported HER electrocatalysts. Given the easy scale-up synthesis due to the stabilization of ultrafine Pt nanoparticles by Co/NC solid ligands, Ptx /Co can even be a promising substitute for commercial Pt/C for practical applications.

Schottky Barrier-Induced Surface Electric Field Boosts Universal Reduction of NOx - in Water to Ammonia.

NOx - reduction acts a pivotal part in sustaining globally balanced nitrogen cycle and restoring ecological environment, ammonia (NH3 ) is an excellent energy carrier and the most valuable product among all the products of NOx - reduction reaction, the selectivity of which is far from satisfaction due to the intrinsic complexity of multiple-electron NOx - -to-NH3 process. Here, we utilize the Schottky barrier-induced surface electric field, by the construction of high density of electron-deficient Ni nanoparticles inside nitrogen-rich carbons, to facilitate the enrichment and fixation of all NOx - anions on the electrode surface, including NO3 - and NO2 - , and thus ensure the final selectivity to NH3 . Both theoretical and experimental results demonstrate that NOx - anions were continuously captured by the electrode with largely enhanced surface electric field, providing excellent Faradaic efficiency of 99 % from both electrocatalytic NO3 - and NO2 - reduction. Remarkably, the NH3 yield rate could reach the maximum of 25.1 mg h-1 cm-2 in electrocatalytic NO2 - reduction reaction, outperforming the maximum in the literature by a factor of 6.3 in neutral solution. With the universality of our electrocatalyst, all sorts of available electrolytes containing NOx - pollutants, including seawater or wastewater, could be directly used for ammonia production in potential through sustainable electrochemical technology.

Electrochemical activation of C-H by electron-deficient W2C nanocrystals for simultaneous alkoxylation and hydrogen evolution.

The activation of C-H bonds is a central challenge in organic chemistry and usually a key step for the retro-synthesis of functional natural products due to the high chemical stability of C-H bonds. Electrochemical methods are a powerful alternative for C-H activation, but this approach usually requires high overpotential and homogeneous mediators. Here, we design electron-deficient W2C nanocrystal-based electrodes to boost the heterogeneous activation of C-H bonds under mild conditions via an additive-free, purely heterogeneous electrocatalytic strategy. The electron density of W2C nanocrystals is tuned by constructing Schottky heterojunctions with nitrogen-doped carbon support to facilitate the preadsorption and activation of benzylic C-H bonds of ethylbenzene on the W2C surface, enabling a high turnover frequency (18.8 h-1) at a comparably low work potential (2 V versus SCE). The pronounced electron deficiency of the W2C nanocatalysts substantially facilitates the direct deprotonation process to ensure electrode durability without self-oxidation. The efficient oxidation process also boosts the balancing hydrogen production from as-formed protons on the cathode by a factor of 10 compared to an inert reference electrode. The whole process meets the requirements of atomic economy and electric energy utilization in terms of sustainable chemical synthesis.