Highly Efficient Nitrogen Reduction to Ammonia through the Cooperation of Plasma and Porous Metal-Organic Framework Reactors with Confined Water.

While the ambient N2 reduction to ammonia (NH3) using H2O as hydrogen source (2N2+6H2O=4NH3+3O2) is known as a promising alternative to the Haber-Bosch process, the high bond energy of N≡N bond leads to the extremely low NH3 yield. Herein, we report a highly efficient catalytic system for ammonia synthesis using the low-temperature dielectric barrier discharge plasma to activate inert N2 molecules into the activated nitrogen species, which can efficiently react with the confined and concentrated H2O molecules in porous metal-organic framework (MOF) reactors with V3+, Cr3+, Mn3+, Fe3+, Co2+, Ni2+ and Cu2+ ions. Specially, the Fe-based catalyst MIL-100(Fe) causes a superhigh NH3 yield of 22.4 mmol g-1 h-1. The investigation of catalytic performance and systematic characterizations of MIL-100(Fe) during the plasma-driven catalytic reaction unveils that the in situ generated defective Fe-O clusters are the highly active sites and NH3 molecules indeed form inside the MIL-100(Fe) reactor. The theoretical calculation reveals that the porous MOF catalysts have different adsorption capacity for nitrogen species on different catalytic metal sites, where the optimal MIL-100(Fe) has the lowest energy barrier for the rate-limiting *NNH formation step, significantly enhancing efficiency of nitrogen fixation.

Plasma-Driven Efficient Conversion of CO2 and H2O into Pure Syngas with Controllable Wide H2/CO Ratios over Metal-Organic Frameworks Featuring In Situ Evolved Ligand Defects.

While the mild production of syngas (a mixture of H2 and CO) from CO2 and H2O is a promising alternative to the coal-based chemical engineering technologies, the inert nature of CO2 molecules, unfavorable splitting pathways of H2O and unsatisfactory catalysts lead to the challenge in the difficult integration of high CO2 conversion efficiency with produced syngas with controllable H2/CO ratios in a wide range. Herein, we report an efficient plasma-driven catalytic system for mild production of pure syngas over porous metal-organic framework (MOF) catalysts with rich confined H2O molecules, where their syngas production capacity is regulated by the in situ evolved ligand defects and the plasma-activated intermediate species of CO2 molecules. Specially, the Cu-based catalyst system achieves 61.9 % of CO2 conversion and the production of pure syngas with wide H2/CO ratios of 0.05 : 1-4.3 : 1. As revealed by the experimental and theoretical calculation results, the in situ dynamic structure evolution of Cu-containing MOF catalysts favors the generation of coordinatively unsaturated metal active sites with optimized geometric and electronic characteristics, the adsorption of reactants, and the reduced energy barriers of syngas-production potential-determining steps of the hydrogenation of CO2 to *COOH and the protonation of H2O to *H.

Regulated Dual Defects of Bridging Organic and Terminal Inorganic Ligands in Iron-based Metal-Organic Framework Nodes for Efficient Photocatalytic Ammonia Synthesis.

Engineering advantageous defects to construct well-defined active sites in catalysts is promising but challenging to achieve efficient photocatalytic NH3 synthesis from N2 and H2O due to the chemical inertness of N2 molecule. Here, we report defective Fe-based metal-organic framework (MOF) photocatalysts via a non-thermal plasma-assisted synthesis strategy, where their NH3 production capability is synergistically regulated by two types of defects, namely, bridging organic ligands and terminal inorganic ligands (OH- and H2O). Specially, the optimized MIL-100(Fe) catalysts, where there are only terminal inorganic ligand defects and coexistence of dual defects, exhibit the respective 1.7- and 7.7-fold activity enhancement comparable to the pristine catalyst under visible light irradiation. As revealed by experimental and theoretical calculation results, the dual defects in the catalyst induce the formation of abundant and highly accessible coordinatively unsaturated Fe active sites and synergistically optimize their geometric and electronic structures, which favors the injection of more d-orbital electrons in Fe sites into the N2 π* antibonding orbital to achieve N2 activation and the formation of a key intermediate *NNH in the reaction. This work provides a guidance on the rational design and accurate construction of porous catalysts with precise defective structures for high-performance activation of catalytic molecules.

Constructing Defective Heterojunctions of BiOBr Nanosheets and Hollow NH2 -functionalized MOFs for Visible-light-driven CO2 Reduction with Nearly 100% CO Selectivity by Pure H2 O.

To rationally design photocatalysts with high generation rate and selectivity of target product remains an ongoing challenge for CO2 conversion in pure H2 O. Herein, from the viewpoint of enhancing the separation efficiency of photoinduced electron-hole pairs and the adsorption ability of CO2 molecule, we have constructed a series of Z-scheme defective heterojunctions of BiOBr nanosheets and hollow NH2 -functionalized metal-organic framework (MOF) MIL-125 with Ti ions as metal centers (noted as NH2 -MIL-125(Ti)). Systematic characterization demonstrates that the BiOBr nanosheets are anchored on the surface of hollow NH2 -MIL-125(Ti), which facilitates the efficient visible-light-driven catalytic reduction of CO2 to CO with nearly 100% selectivity by pure H2 O. Especially, the CO generation rate of optimized catalyst with oxygen vacancies reaches 459.7 µmol g-1 h-1 , which is higher than those of all the previously reported photocatalysts without sacrificial reagents. This approach provides a new insight for using inorganic semiconductors to fabricate semiconducting MOFs for high-efficiency photocatalytic reduction CO2 into value-added chemicals by pure H2 O.

Large-Scale Silver Sulfide Nanomesh Membranes with Ultrahigh Flexibility.

The growth of flexible semiconductor thin films and membranes is highly desirable for the fabrication of next-generation wearable devices. In this work, we have developed a one-step, surface tension-driven method for facile and scalable growth of silver sulfide (Ag2S) membranes with a nanomesh structure. The nanomesh membrane can in principle reach infinite size but only limited by the reactor size, while the thickness is self-limited to ca. 50 nm. In particular, the membrane can be continuously regenerated at the water surface after being transferred for mechanical and electronic tests. The free-standing membrane demonstrates exceptional flexibility and strength, resulting from the nanomesh structure and the intrinsic plasticity of the Ag2S ligaments, as revealed by robust manipulation, nanoindentation tests and a pseudo-in situ tensile test under scanning electron microscope. Bendable electronic resistance-switching devices are fabricated based on the nanomesh membrane.

A green synthesis approach toward large-scale production of benzalacetone via Claisen-Schmidt condensation.

Claisen-Schmidt (CS) condensation between acetone and benzaldehyde with NaOH as the catalyst is a well-recognized pathway for the synthesis of benzalacetone (BA). However, this process is compromised by a side reaction, i.e., a second CS reaction between benzaldehyde and the BA product. In this work, we designed a stirring-induced emulsion synthesis technique for the cyclic and scaling-up production of BA with 99 ± 1% selectivity, without the use of surfactants. In this approach, the water-soluble acetone and NaOH were separated from the oil-soluble benzaldehyde by the organic-aqueous phase interface, such that the CS condensation could only be executed at the liquid interface. The just-formed BA molecules diffuse to the interior of the oil solvent, where any subsequent CS post-reaction is rendered negligible, owing to the absence of NaOH. The oil phase containing the BA molecules can be easily separated from the aqueous solution by stopping stirring and undisturbed standing, allowing for a large-scale production protocol. As a proof of concept, over 1 kg of BA was produced in the laboratory with high yield and purity.

Unconventional, Gram-Scale Synthesis of a Molecular Dimer Organic Luminogen with Aggregation-Induced Emission.

Organic luminogens have been widely used in optoelectronic devices, bioimaging, and sensing. Conventionally, the synthesis of organic luminogens requires sophisticated, multistep design, reaction, and isolation procedures. Herein, the products of the melt-phase condensation of benzoguanamine (BG; 2,4-diamino-6-phenyl-1,3,5-triazine) at 370-410 °C display interesting reaction-condition-dependent luminescence properties, including photoluminescence (PL) at a variety of wavelengths in the visible spectrum and quantum efficiencies (PLQE) of up to 58% in the powder form. With a simple and straightforward solvent washing procedure, the prominent blue luminescent component BG dimer was obtained in gram scale with >93% purity (96.5% purity after fractional sublimation). The BG dimer exhibited distinct aggregation-induced emission (AIE) properties. PL measurements indicate that the electronically excited state of the BG dimer undergoes efficient intramolecular nonradiative deactivation in room-temperature solution, leading to a significantly reduced PLQE (<0.1%) in solution. These nonradiative processes are substantially inhibited when the dimer existed in the form of crystals, solid aggregates in solution or being fixed in a rigid polymer film, resulting in a significant increase in the PLQE and lifetime. This work not only provided a new understanding for PL properties of self-condensation luminescent products but also represented an unconventional strategy for large-scale preparation of organic luminogens with high purity.

A bioinspired microreactor with interfacial regulation for maximizing selectivity in a catalytic reaction.

We report a bioinspired emulsion microreactor composed of an electrical double layer to mimic the functions of cell membranes. This "artificial cell" can modulate the phase-oriented transport of reagents at the oil-liquid interface via the electrical double layer, affording a powerful tool to optimize the selectivity in a catalytic reaction.

Crystal Transformation from the Incorporation of Coordinate Bonds into a Hydrogen-Bonded Network Yields Robust Free-Standing Supramolecular Membranes.

In this work, we report on the synthesis of a free-standing, macroscopic robust supramolecular membrane by introducing silver-nitrogen coordinate bonding into preorganized, supramolecular hydrogen-bonded cyanuric acid-melamine (CAM) crystals. With the assistance of ammonia, silver ions competitively replace two of the three hydrogen atoms from cyanuric acid resulting in the transformation from short CAM nanorods to long CAM-Ag nanofibers (length over 1000 µm), accompanied by tautomerization of cyanuric acid. The single crystal structure of the CAM-Ag nanofibers is solved in the space group P1, with the asymmetric unit containing eight silver atoms, four melamine and four cyanuric acid molecules, which generate 1D coordination polymer chains consisting of alternating melamine and dianionic cyanurate ligands linked via silver-nitrogen bonds. The presence of interchain hydrogen bonds results in the expansion of the supramolecular network into undulating 2D sheets, which then stack into a 3D network via a series of intersheet hydrogen bonds and π-π interactions. Significantly, the CAM-Ag nanofibers spontaneously assemble into a free-standing membrane, with lateral size up to square centimeters and thickness of 30 µm. The membrane shows high flexibility and mechanical strength, owing to the improved flexibility of the CAM-Ag nanofibers with bonded chain structure, and can be reversibly and repeatedly bent over 90 degrees. Remarkably, the CAM-Ag membrane demonstrates distinct optical transmittance being shortwave IR transmissive but impenetrable to UV and visible light.

A photothermal reservoir for highly efficient solar steam generation without bulk water.

A solid photothermal reservoir is designed to implement solar-steam generation in the absence of bulk water. The photothermal reservoir is composed of a water absorbing core encapsulated by a photothermal reduced graphene oxide based aerogel sheet which absorbs light and converts it into heat thus evaporating the stored water. The photothermal reservoir is able to store 6.5 times its own weight in water, which is sufficient for one day solar evaporation, thus no external water supplement is required. During solar-steam generation, since no bulk water is involved, the photothermal reservoir minimizes heat conduction loss, and maximizes both of the exposed evaporation surface area and net energy gain from the environment, leading to an energy efficiency beyond the theoretical limit. An extremely high water evaporation rate of 4.0 kg m-2 h-1 (normalized to projection area) is achieved in laboratory studies over a cylinder photothermal reservoir with a diameter of 5.2 cm and a height of 15 cm under 1.0 sun irradiation. Practical evaluation of the photothermal reservoir outdoors as part of a desalination device demonstrates a similar evaporation rate where the salinity of the clean water produced is lower than 24 ppb. Thus the photothermal reservoir shows great potential for real world applications in portable solar-thermal desalination.

Palladium/Graphitic Carbon Nitride (g-C3 N4 ) Stabilized Emulsion Microreactor as a Store for Hydrogen from Ammonia Borane for Use in Alkene Hydrogenation.

Direct hydrogenation of C=C double bonds is a basic transformation in organic chemistry which is vanishing from simple practice because of the need for pressurized hydrogen. Ammonia borane (AB) has emerged as a hydrogen source through its safety and high hydrogen content. However, in conventional systems the hydrogen liberated from the high-cost AB cannot be fully utilized. Herein, we develop a novel Pd/g-C3 N4 stabilized Pickering emulsion microreactor, in which alkenes are hydrogenated in the oil phase with hydrogen originating from AB in the water phase, catalysed by the Pd nanoparticles at the interfaces. This approach is advantageous for more economical hydrogen utilization over conventional systems. The emulsion microreactor can be applied to a range of alkene substrates, with the conversion rates achieving >95 % by a simple modification.

Direct Observation of Carbon Nitride-Stabilized Pickering Emulsions.

Pickering emulsions are emulsions stabilized by solid particles located at surfaces/interfaces of liquid droplets that have promising applications for drug delivery and in nanomaterials synthesis. Direct observation of Pickering emulsions can be challenging. Normally, cryoelectron microscopy needs to be used to better understand these types of emulsion systems, but cryofreezing these emulsions may cause them to lose their original morphologies. In this work, we demonstrate that graphitic carbon nitride (g-C3N4) can stabilize oil-in-water (o/w) emulsions, with hexane illustrated as a typical oil phase. The g-C3N4-stabilized emulsions can act as an excellent platform for in situ study of emulsifying behavior from the mechanical point of view. Owing to its large lateral size and blue, stable fluorescence, the locations and motions of the g-C3N4 stabilizer can be finely in situ monitored by light microscopy, fluorescence microscopy, and confocal microscopy. Accordingly, we illustrate two stabilizing configurations of the g-C3N4 particles with respect to the emulsion droplets under static conditions. Further, we demonstrate the capability to manipulate emulsion droplets and investigate their response to external forces. We perform real-time observations of the g-C3N4 particles and the emulsion droplets that move in the continuous phase and study their adsorption kinetics toward each other. Finally, the π-π interaction between the stabilizer and aromatic liquid phase (e.g., toluene) is considered and studied as an influencing factor on emulsifying behavior.

Covalent Functionalization of Carbon Nitride Frameworks through Cross-Coupling Reactions.

A new and simple synthetic route is introduced to covalently functionalize the carbon nitride (CN) framework by the implementation of halogenated phenyl groups (Cl, Br and I), which serve as a chemically reactive center, within the CN framework. The covalent modification is demonstrated here by substituting phenyl and tert-butyl propionate onto the modified-CN framework through Suzuki and reductive-Heck cross-coupling reactions, respectively. The effective functionalization leads to a facile exfoliation of the CN framework into thinner layers and greatly enhances the dispersibility in many solvents as well as the photocatalytic activity compared to the unmodified CN. The general covalent modification opens the possibility for tailor-made design of dispersible CN materials, including their photophysical and chemical properties, toward their exploitation in many fields, such as photocatalysis, bio-imaging, sensing, and heterogeneous catalysis.

Graphitic Carbon Nitride as a Distinct Solid Stabilizer for Emulsion Polymerization.

g-C3 N4 has been found to be highly functional in many fields, such as photocatalysis, electrocatalysis, and chemical analysis. Pickering emulsion polymerization is a fascinating strategy to fabricate a range of nanomaterials, in which the emulsion is stabilized by solid particles, rather than molecular surfactants. Herein, we demonstrate that g-C3 N4 can act as a remarkable stabilizer for Pickering emulsion polymerization. Contrary to normal Pickering systems, monodisperse polystyrene microspheres with tunable size, surface charge, and morphology were achieved using this approach. Importantly, the g-C3 N4 hybridized latex is highly processable and has exhibited multiple functions: manufacture of photonic crystals via self-organization, stabilizing Pickering emulsion owing to proper wettability, and acting as bioimaging agents with enriched fluorescent colors. Considering the easy synthesis and low cost of g-C3 N4 , our approach has a high potential for scale-up synthesis and practical translation.

Silver and palladium alloy nanoparticle catalysts: reductive coupling of nitrobenzene through light irradiation.

Silver-palladium (Ag-Pd) alloy nanoparticles strongly absorb visible light and exhibit significantly higher photocatalytic activity compared to both pure palladium (Pd) and silver (Ag) nanoparticles. Photocatalysts of Ag-Pd alloy nanoparticles on ZrO2 and Al2O3 supports are developed to catalyze the nitroaromatic coupling to the corresponding azo compounds under visible light irradiation. Ag-Pd alloy NP/ZrO2 exhibited the highest photocatalytic activity for nitrobenzene coupling to azobenzene (yield of ∼80% in 3 hours). The photocatalytic efficiency could be optimized by altering the Ag : Pd ratio of the alloy nanoparticles, irradiation light intensity, temperature and wavelength. The rate of the reaction depends on the population and energy of the excited electrons, which can be improved by increasing the light intensity or by using a shorter wavelength. The knowledge developed in this study may inspire further studies on Ag alloy photocatalysts and organic syntheses using Ag-Pd nanoparticle catalysts driven under visible light Irradiation.