Anomalously enhanced ion transport and uptake in functionalized angstrom-scale two-dimensional channels.

Emulating angstrom-scale dynamics of the highly selective biological ion channels is a challenging task. Recent work on angstrom-scale artificial channels has expanded our understanding of ion transport and uptake mechanisms under confinement. However, the role of chemical environment in such channels is still not well understood. Here, we report the anomalously enhanced transport and uptake of ions under confined MoS2-based channels that are ~five angstroms in size. The ion uptake preference in the MoS2-based channels can be changed by the selection of surface functional groups and ion uptake sequence due to the interplay between kinetic and thermodynamic factors that depend on whether the ions are mixed or not prior to uptake. Our work offers a holistic picture of ion transport in 2D confinement and highlights ion interplay in this regime.

Unravelling the Photoelectrochemical Water Splitting of Nanometer-Thick Carbon Nitride Layer.

Matching the thickness of the graphitic carbon nitride (CN) nanolayer with the charge diffusion length is expected to compensate for the poor intrinsic conductivity and charge recombination in CN for photoelectrochemical cells (PEC). Herein, the compact CN nanolayer with tunable thickness is in situ coated on carbon fibers. The compact packing along with good contact with the substrate improves the electron transport and alleviates the charge recombination. The PEC investigation shows CN nanolayer of 93 nm-thick yields an optimum photocurrent of 116 µA cm-2 at 1.23 V versus RHE, comparable to most micrometer-thick CN layers, with a low onset potential of 0.2 V in 1 m KOH under 1 sun illumination. This optimum performance suggests the electron diffusion length matches with the thickness of the CN nanolayer. Further deposition of NiFe-layered double hydroxide enhanced the surface water oxidation kinetics, delivering an improved photocurrent of 210 µA cm-2 with IPCE of 12.8% at 400 nm. The CN nanolayer also shows extended potential in PEC organic synthesis. This work experimentally reveals the PEC behavior of the nanometer-thick CN layer, providing new insights into CN in the application of energy and environment-related fields.

Hydrophobic Carbon Nitride Nanolayer Enables High-Flux Oil/Water Separation with Photocatalytic Antifouling Ability.

Efficient oil/water separation tackles various issues in occasions of oil leakage and oil discharge, such as environmental pollution, recollection of the oil, and saving the water. Herein, a compact superhydrophobic/superoleophilic graphitic carbon nitride nanolayer coated on carbon fiber networks (CNBA/CF) is designed and synthesized for efficient gravity-driven oil/water separation. The CNBA/CF shows excellent oil absorption and an impressive oil/water filtration separation performance. The flux reaches the state-of-art value of 4.29 × 105 L/m2/h for dichloromethane with separation efficiency up to 99%. Successive oil absorption tests, long-term filtration separation, and harsh conditions experiments confirm the remarkable separation and chemical structure stability of the CNBA/CF filter. Besides, the CNBA/CF demonstrates good photocatalytic antifouling ability thanks to the extended visible light absorption and improved charge separation. This work combines the material surface wettability modulation with a photocatalytic self-cleaning property in the fabrication of efficient oil/water separation materials while overcoming the filter fouling issue.

Nitrogen-Defective Polymeric Carbon Nitride Nanolayer Enabled Efficient Electrocatalytic Nitrogen Reduction with High Faradaic Efficiency.

Identifying highly selective catalysts and accurately measuring NH3 yield without false-positives from contaminations remain two challenges in electrochemical nitrogen reduction reaction (NRR). Here, we report N-defective carbon nitride grown on carbon paper (CN/C) as a highly selective electrocatalyst. The NH3 yield was determined reliably by the slope of mNH3-time plot rather than averaging the accumulated amount over time. Results showed the as-synthesized CN/C600 (synthesized at 600 °C) with a higher density of C=N-C N2C vacancies achieved an NH3 production of 2.9 µg mgcat.-1 h-1 at -0.3 V (versus RHE), ∼5.7-fold higher than CN/C500. The Faradaic efficiency for CN/C600 is among the highest of 62.1%, 33.9%, and 16.8% at -0.1 V, -0.2 V, and -0.3 V, respectively. The NH3 production was verified by isotope 15N2 experiments. Further increase of N-defects on CN/C600 using plasma etching led to higher NH3 yield than comparably larger current, pointing to N-defects sites for promoting NRR.

Carbon Nitride Materials for Water Splitting Photoelectrochemical Cells.

Graphitic carbon nitride materials (CNs) have emerged as suitable photocatalysts and heterogeneous catalysts for various reactions thanks to their tunable band gap, suitable energy-band position, high stability under harsh chemical conditions, and low cost. However, the utilization of CN in photoelectrochemical (PEC) and photoelectronic devices is still at an early stage owing to the difficulties in depositing high-quality and homogenous CN layer on substrates, its wide band gap, poor charge-separation efficiency, and low electronic conductivity. In this Minireview, we discuss the synthetic pathways for the preparation of various structures of CN on substrates and their underlying photophysical properties and current photoelectrochemical performance. The main challenges for CN incorporation into PEC cell are described, together with possible routes to overcome the standing limitations toward the integration of CN materials in PEC and other photoelectronic devices.

Unprecedented Centimeter-Long Carbon Nitride Needles: Synthesis, Characterization and Applications.

Free standing centimeter-long 1D nanostructures are highly attractive for electronic and optoelectronic devices due to their unique photophysical and electrical properties. Here a simple, large-scale synthesis of centimeter-long 1D carbon nitride (CN) needles with tunable photophysical, electric, and catalytic properties is reported. Successful growth of ultralong needles is acquired by the utilization of 1D organic crystal precursors comprised of CN monomers as reactants. Upon calcination at high temperatures, the shape of the starting crystal is fully preserved while the CN composition and porosity, and optical and electrical properties can be easily tuned by tailoring the starting elements ratio and final calcination temperature. The facile manipulation and visualization of the CN needles endow their direct electrical measurements by placing them between two conductive probes. Moreover, the CN needles exhibit good photocatalytic activity for hydrogen production owing to their improved light harvesting properties, high surface area, and advantageous energy bands position. The new growth strategy developed here may open opportunities for a rational design of CN and other metal-free materials with controllable directionality and tunable photophysical and electronic properties, toward their utilization in (photo)electronic devices.

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.

A Water-Splitting Carbon Nitride Photoelectrochemical Cell with Efficient Charge Separation and Remarkably Low Onset Potential.

A simple method to grow a closely packed carbon nitride (CN) film by the crystallization of CN monomers on a conductive substrate followed by a thermal condensation is reported. The as-synthesized CN exhibits excellent performance as photoanode material in a photoelectrochemical cell. Detailed (photo)electrochemical and transient absorption measurements indicate excellent charge separation properties, high hole-extraction efficiency (up to 50 %), a long electron lifetime, and low amount of defect states below the CN conduction band. Consequently, the CN photoanode exhibits a markedly low overpotential of 0.25 V versus reversible hydrogen electrode (RHE), which is comparable with the state-of-the-art metal-based photoanodes, an impressive photocurrent density of 116 µA cm-2 at 1.23 V versus RHE in an alkaline solution without sacrificial agent, as well as excellent stability over a wide pH range (0-13).

A General Synthesis of Porous Carbon Nitride Films with Tunable Surface Area and Photophysical Properties.

Graphitic carbon nitride (g-CN) has emerged as a promising material for energy-related applications. However, exploitation of g-CN in practical devices is still limited owing to difficulties in fabricating g-CN films with adjustable properties and high surface area. A general and simple pathway is reported to grow highly porous and large-scale g-CN films with controllable chemical and photophysical properties on various substrates using the doctor blade technique. The growth of g-CN films, ascribed to the formation of a supramolecular paste, comprises g-CN monomers in ethylene glycol, which can be cast on different substrates. The g-CN composition, porosity, and optical properties can be tuned by the design of the supramolecular paste, which upon calcination results in a continuous porous g-CN network. The strength of the porous structure is demonstrated by high electrochemically active surface area, excellent dye adsorption and photoelectrochemical and photodegradation properties.

Lanthanide transport in angstrom-scale MoS2-based two-dimensional channels.

Rare earth elements (REEs), critical to modern industry, are difficult to separate and purify, given their similar physicochemical properties originating from the lanthanide contraction. Here, we systematically study the transport of lanthanide ions (Ln3+) in artificially confined angstrom-scale two-dimensional channels using MoS2-based building blocks in an aqueous environment. The results show that the uptake and permeability of Ln3+ assume a well-defined volcano shape peaked at Sm3+. This transport behavior is rooted from the tradeoff between the barrier for dehydration and the strength of interactions of lanthanide ions in the confinement channels, reminiscent of the Sabatier principle. Molecular dynamics simulations reveal that Sm3+, with moderate hydration free energy and intermediate affinity for channel interaction, exhibit the smallest dehydration degree, consequently resulting in the highest permeability. Our work not only highlights the distinct mass transport properties under extreme confinement but also demonstrates the potential of dialing confinement dimension and chemistry for greener REEs separation.

Surface Valence State Effect of MoO2+x on Electrochemical Nitrogen Reduction.

The valance of Mo is critical for FeMo cofactor in ambient ammonia synthesis. However, the valence effect of Mo has not been well studied in heterogeneous nanoparticle catalysts for electrochemical nitrogen reduction reaction (NRR) due to the dissolution of Mo as MoO42- in alkaline electrolytes. Here, a MoO2+x catalyst enriched with surface Mo6+ is reported. The Mo6+ is stabilized by a native oxide layer to prevent corrosion and its speciation is identified as (MoO3 )n clusters. This native layer with Mo6+ suppresses the hydrogen evolution significantly and promotes the activation of nitrogen as supported by both experimental characterization and theoretical calculation. The as-prepared MoO2+x catalyst shows a high ammonia yield of 3.95 µg mgcat-1 h-1 with a high Faradaic efficiency of 22.1% at -0.2 V versus reversible hydrogen electrode, which is much better than the MoO2 catalyst with Mo6+ etched away. The accuracy of experimental results for NRR is confirmed by various control experiments and quantitative isotope labeling.

Tuning transport in graphene oxide membrane with single-site copper (II) cations.

Controlling the ion transport through graphene oxide (GO) membrane is challenging, particularly in the aqueous environment due to its strong swelling tendency. Fine-tuning the interlayer spacing and chemistry is critical to create highly selective membranes. We investigate the effect of single-site divalent cations in tuning GO membrane properties. Competitive ionic permeation test indicates that Cu2+ cations dominate the transport through the 2D channels of GO membrane over other cations (Mg2+/Ca2+/Co2+). Without/With the single-site M2+ modifications, pristine GO, Mg-GO, Ca-GO, and Cu-GO membranes show interlayer spacings of ∼13.6, 15.6, 14.5, and 12.3 Å in wet state, respectively. The Cu-GO membrane shows a two-fold decrease of NaCl (1 M) permeation rate comparing to pristine GO, Mg-GO, and Ca-GO membranes. In reverse osmosis tests using 1000 ppm NaCl and Na2SO4 as feeds, Cu-GO membrane shows rejection of ∼78% and ∼94%, respectively, which are 5%-10% higher than its counterpart membranes.

Direct growth of uniform carbon nitride layers with extended optical absorption towards efficient water-splitting photoanodes.

A general synthesis of carbon nitride (CN) films with extended optical absorption, excellent charge separation under illumination, and outstanding performance as a photoanode in water-splitting photoelectrochemical cells is reported. To this end, we introduced a universal method to rapidly grow CN monomers directly from a hot saturated solution on various substrates. Upon calcination, a highly uniform carbon nitride layer with tuned structural and photophysical properties and in intimate contact with the substrate is obtained. Detailed photoelectrochemical and structural studies reveal good photoresponse up to 600 nm, excellent hole extraction efficiency (up to 62%) and strong adhesion of the CN layer to the substrate. The best CN photoanode demonstrates a benchmark-setting photocurrent density of 353 µA cm-2 (51% faradaic efficiency for oxygen), and external quantum yield value above 12% at 450 nm at 1.23 V versus RHE in an alkaline solution, as well as low onset potential and good stability.

Photo-reduction enables catalyst regeneration in Fenton reaction on an Fe2O3-decorated TiO2 nanotube-based photocatalyst.

The Fenton reaction is regarded as an advanced oxidation process that can efficiently remediate environmental pollutants. However, the one-time irreversible consumption of its catalysts raises the cost in practical application. Herein, we report the generation of active Fe2+ sites via photo-reduction by photogenerated electrons on a TiO2 nanotube-based catalyst (TNT(Pd)/Fe2O3) with Fe2O3 decorated on the outside wall, while the inside cavity entrapped Pd nanoparticles. Fenton catalytic investigations under visible light show that TNT(Pd)/Fe2O3 displays superior methyl orange degradation activity with 90% removal in 10 minutes. The kinetic constant is 4.3 times as the sum of the pure photocatalysis and Fenton catalytic kinetic constants. The synergistic effect between the Fenton and photocatalytic reactions is further evidenced by the photocurrent and photodegradation tests. The TNT(Pd)/Fe2O3 catalyst showed no decay in the Fenton-photocatalytic performance over three successive cycles. XPS measurements after long-term stability tests revealed no loss, but a slight increase in the number of Fe2+ species. All of these results suggest that the most active Fe2+ species in the Fenton reaction can be regenerated via the reduction by photogenerated electrons. This work addressed the challenge in catalyst regeneration in the traditional Fenton reaction via photoreduction by rational combination with a photocatalyst and the realized synergistic effect between photocatalysis and the Fenton reaction.

Freestanding Hierarchical Carbon Nitride/Carbon-Paper Electrode as a Photoelectrocatalyst for Water Splitting and Dye Degradation.

Freestanding electrodes composed of 2D materials are highly attractive for many applications such as batteries, membranes, actuators, optical devices, and other energy-related devices owing to their low price, unique structure, high specific surface area, and excellent mechanical and electrical properties. Here, we report the facile large-scale fabrication of freestanding hierarchical carbon nitride/carbon electrodes (CN/C) by the in situ crystallization of CN precursors on conductive carbon paper, followed by thermal annealing. The resulting CN exhibits a vertically aligned morphology with a homogeneous layer distribution, improved crystallinity, and excellent contact with the carbon paper. The freestanding electrodes exhibit high electrical conductivity and good photoelectrochemical activity as anodes in water splitting photoelectrochemical cells. Furthermore, we show here as a proof-of-concept that the freestanding CN/C electrodes can be used as photoelectrocatalysts for the oxidative degradation of organic compounds in water, with enhanced activity compared to photocatalytic and electrocatalytic degradation, while the extracted electrons can be used for the simultaneous production of hydrogen at the cathode.

Tailoring carbon nitride properties and photoactivity by interfacial engineering of hydrogen-bonded frameworks.

The rational synthesis of carbon nitride materials, ranging from polymeric carbon nitride to nitrogen-doped carbon, by supramolecular preorganization of their monomers is a powerful tool for the design of their morphology and photophysical and catalytic activities. Here we show a new facile and scalable approach for the synthesis of ordered CN materials with excellent photoactivity, which consists of supramolecular interfacial preorganization of CN monomers at the interface of two non-miscible solvents. Molecular dynamic simulations supported by experimental results reveal that an appropriate choice of monomers and solvents leads to the formation of a supramolecular assembly solely at the interface of the solvents. As a proof of concept, we show that the properties of the CN materials after thermal condensation can be tuned by adding an additional monomer to one solvent only. The advantages of the new method are demonstrated here through the tunable morphologies and surface area, the formation of new electronic junctions and high activity as a photocatalyst for hydrogen evolution and pollutant degradation of the CN materials.

Low-Cost Porous Ruthenium Layer Deposited on Nickel Foam as a Highly Active Universal-pH Electrocatalyst for the Hydrogen Evolution Reaction.

Low-cost and high-efficiency electrocatalysts for the hydrogen evolution reaction (HER) are a key constituent of a low-carbon industrial economy based on intermittent energy production in the near future. A facile wet-chemistry strategy has been developed for the synthesis of a porous Ru layer deposited onto Ni foam (NF) as a competitive candidate for HER over the whole pH range, especially under economical alkaline conditions. The catalyst shows outstanding HER performance, which stems from the porosity of the Ru layer, the electronic structure of the electrode, and the charge transfer between the NF and the Ru layer, which gives rise to the strong activity of the Ru layer in the HER process. Moreover, the Ru loading was as low as approximately 1.1 wt %, representing significant potential for application in cost-effective HER.

Layered Boron-Nitrogen-Carbon-Oxygen Materials with Tunable Composition as Lithium-Ion Battery Anodes.

The insertion of heteroatoms with different electronegativity into carbon materials can tune their chemical, electronic, and optical properties. However, in traditional solid-state synthesis, it is challenging to control the reactivity of monomers, and therefore, the amount and position of heteroatoms in the final materials. Herein, a simple, scalable, and general molten-state route to synthesize boron-nitrogen-carbon-oxygen (BNCO) materials with tunable boron-nitrogen-carbon composition, as well as electronic and optical properties, is reported. The new synthetic approach consists of polycyclic aromatic hydrocarbons (PAHs) and ammonia-borane as reactants that form a clear liquid-state stage spanning a wide temperature range, before the solid-state reaction. The molten-state stage enhances the control over the synthetic intermediates and final materials, owing to improved monomer miscibility and reactivity. The BNCO composition and optical properties are tuned by the PAH selection and final reaction temperature. The advantages of this method are demonstrated herein through the tunable optical properties, excellent stability to oxidization, facile deposition on substrates, and good activity as an anode material in lithium-ion batteries.

In Situ Grown TiO2 Nanospindles Facilitate the Formation of Holey Reduced Graphene Oxide by Photodegradation.

Titanium dioxide (TiO2) nanostructures and TiO2/graphene nanocomposites are intensively studied materials for energy conversion, energy storage, and organic contaminant photodegradation. However, for TiO2/graphene composites, impermeability across the graphitic basal plane for electrolytes, metal ions, and gas molecules hinders their practical applications. Herein we report a simple, environmentally friendly synthetic route for mesoporous anatase TiO2 nanospindles, and successfully apply this method to obtain in situ grown TiO2 nanospindles/graphene oxide composite. After a thermal reduction at 400 °C, holes are created in the reduced graphene oxide (RGO) sheets through a photocatalytic oxidation mechanism. The formation of holes in RGO is promoted by photogenerated hydroxyl radicals that oxidize and subsequently decarboxylate the graphitic surface of RGO. The proposed mechanism was supported by photocatalytic electrochemical properties of the nanomaterials. The resulting TiO2/holey RGO composites may overcome the original impermeability of graphene sheets and find applications in catalysis, energy conversion/storage devices, and sensors.

Binding characteristics of homogeneous molecularly imprinted polymers for acyclovir using an (acceptor-donor-donor)-(donor-acceptor-acceptor) hydrogen-bond strategy, and analytical applications for serum samples.

This paper demonstrates a novel approach to assembling homogeneous molecularly imprinted polymers (MIPs) based on mimicking multiple hydrogen bonds between nucleotide bases by preparing acyclovir (ACV) as a template and using coatings grafted on silica supports. (1)H NMR studies confirmed the AAD-DDA (A for acceptor, D for donor) hydrogen-bond array between template and functional monomer, while the resultant monodisperse molecularly imprinted microspheres (MIMs) were evaluated using a binding experiment, high performance liquid chromatography (HPLC), and solid phase extraction. The Langmuir isothermal model and the Langmuir-Freundlich isothermal model suggest that ACV-MIMs have more homogeneous binding sites than MIPs prepared through normal imprinting. In contrast to previous MIP-HPLC columns, there were no apparent tailings for the ACV peaks, and ACV-MIMs had excellent specific binding properties with a Ka peak of 3.44 × 10(5)M(-1). A complete baseline separation is obtained for ACV and structurally similar compounds. This work also successfully used MIMs as a specific sorbent for capturing ACV from serum samples. The detection limit and mean recovery of ACV was 1.8 ng/mL(-1) and 95.6%, respectively, for molecularly imprinted solid phase extraction coupled with HPLC. To our knowledge, this was the first example of MIPs using AAD-DDA hydrogen bonds.