Photosynthetic-Membrane-Like Ion Translocation in Visible-Light-Harvesting Nanofluidic Channels.

The selective uphill and downhill movement of protons in and out of photosynthetic membrane enabled by ion pumps and ion channels is key to photosynthesis. Reproducing the functions of photosynthetic membranes in artificial systems has been a persistent goal. Here, a visible-light-harvesting nanofluidic channels is reported which experimentally demonstrates the ion translocation functions of photosynthetic membranes. A molecular junction consisting of photosensitive ruthenium complexes linked to TiO2 electron acceptors forms the reaction centers in the nanofluidic channels. The visible-light-triggered vectorial electron injection into TiO2 establishes a difference in transmembrane potential across the channels, which enables uphill transport of ions against a 5-fold concentration gradient. In addition, the asymmetric charge distribution across the channels enables the unidirectional downhill movement of ions, demonstrating an ion rectification effect with a ratio of 18:1. This work, for the first time, mimics both the uphill and downhill ion translocation functions of photosynthetic membranes, which lays a foundation for nanofluidic energy conversion.

Nano-Confined Effect and Heterojunction Promoted Exciton Separation for Light-Boosted Osmotic Energy Conversion.

The osmotic energy conversion properties of biomimetic light-stimulated nanochannels have aroused great interest. However, the power output performance is limited by the low light-induced current and energy conversion efficiency. Here, nanochannel arrays with simultaneous modification of ZnO and di-tetrabutylammonium cis-bis(isothiocyanato)bis(2,20-bipyridyl-4,40-dicarboxylato) ruthenium (II) (N719) onto anodic aluminum oxide (AAO) to combine the nano-confined effect and heterojunction is designed, which demonstrate rectified ion transport behavior due to the asymmetric composition, structure and charge. High cation selectivity and ion flux contribute to the high power density of ≈7.33 W m-2 by mixing artificial seawater and river water. Under light irradiation, heterojunction promoted the production and separation of exciton, enhanced cation selectivity, and improved the utilization efficiency of osmotic energy, providing a remarkable power density of ≈18.49 W m-2 with an increase of 252% and total energy conversion efficiency of 30.43%. The work opens new insights into the biomimetic nanochannels for high-performance energy conversion.

Room-Temperature Synthesis of a COFs Membrane Via LBL Self-Assembly Strategy for Energy Harvesting.

The covalent organic frameworks (COFs) membrane with ordered and confined one-dimensional channel has been considered as a promising material to harvest the salinity gradient energy from the seawater and river water. However, the application of the COFs in the field of energy conversion still faces the challenges in membrane preparation. Herein, energy harvesting is achieved by taking advantage of a COFs membrane where TpDB-HPAN is synthesized via layer-by-layer self-assembly strategy at room temperature. The carboxy-rich TpDB COFs can be expediently assembled onto the substrate with an environmental-friendly method. The increased open-circuit voltage (Voc ) endows TpDB-HPAN membrane with a remarkable energy harvesting performance. More importantly, the application perspective is also illuminated by the cascade system. With the advantages of green synthesis, the TpDB-HPAN membrane can be considered as a low-cost and promising candidate for energy conversion.

Brain Wave-Like Signal Modulator by Ionic Nanochannel Rectifier Bridges.

Smart modulation of bioelectric signals is of great significance for the development of brain-computer interfaces, bio-computers, and other technologies. The regulation and transmission of bioelectrical signals are realized through the synergistic action of various ion channels in organisms. The bionic nanochannels, which have similar physiological working environment and ion rectification as their biological counterparts, can be used to construct ion rectifier bridges to modulate the bioelectric signals. Here, the artificial smart ionic rectifier bridge with light response is constructed by anodic aluminum oxide (AAO)/poly (spiropyran acrylate) (PSP) nanochannels. The output ion current of the rectifier bridge can be switched between "ON" and "OFF" states by irradiation with UV and visible (Vis) light, and the conversion efficiency (η) of the system in "ON" state is ≈70.5%. The controllable modulation of brain wave-like signal can be realized by ionic rectifier bridge. The ion transport properties and processes of ion rectifier bridges are explained using theoretical calculations based on Poisson-Nernst-Planck (PNP) equations. These findings have significant implications for the understanding of the intelligent ionic circuit and combination of artificial smart ionic channels to organisms, which provide new avenues for development of intelligent ion devices.

Cation-Selective Oxide Semiconductor Mesoporous Membranes for Biomimetic Ion Rectification and Light-Powered Ion Pumping.

Artificial membranes precisely imitating the biological functions of ion channels and ion pumps have attracted significant attention to explore nanofluidic energy conversion. Herein, inspired by the cyclic ion transport for the photosynthesis in purple bacteria, a bilayer inorganic membrane (TiO2 /AAO) composed of oxide semiconductor (TiO2 ) mesopores on anodic alumina (AAO) macropores is we developed. This inorganic membrane achieves the functions of ion channels and ion pumps, including the ion rectification and light-powered ion pumping. The asymmetric charge distribution across the bilayer membrane contributes to the cationic selectivity and ion rectification characteristics. The electrons induced by ultraviolet irradiation introduce a built-in electric field across TiO2 /AAO membrane, which pumps the active ion transport from a low to a high concentration. This work integrates the functions of biological ion channels and ion pumps within an artificial membrane for the first time, which paves the way to explore multifunctional membranes analogous to its biological counterpart.

Large-Area Covalent Organic Polymers Membrane via Sol-Gel Approach for Harvesting the Salinity Gradient Energy.

Many materials with nanofluidic channels are exploited to achieve salinity gradient energy conversion. However, most materials are fragile, difficult to process, or only prepared into a limited size, which greatly restricts their practical application in the future. Herein, a covalent organic polymers membrane with high mechanical property and stability is fabricated, which can keep integrity in harsh conditions for up to 1 month. In addition, by using the sol-gel approach, a large-area membrane with an area of 26 × 26 cm is expediently fabricated in lab conditions. When the membrane is applied to salinity gradient energy conversion, the maximum output power density is up to 6.21 W m-2 . This work provides a simple method for the fabrication of large-area membrane for salinity gradient energy conversion in future real-world applications.

Light-Powered Ion Pumping in a Cation-Selective Conducting Polymer Membrane.

The simulation of the ion pumping against a proton gradient energized by light in photosynthesis is of significant importance for the energy conversion in a non-biological environment. Herein, we report light-powered ion pumping in a polystyrene sulfonate anion (PSS) doped polypyrrole (PPy) conducting polymer membrane (PSS-PPy) with a symmetric geometry. This PSS-PPy conducting polymer membrane exhibits a cationic selectivity and a light-responsive surface-charge-governed ion transport attributed to the negatively charged PSS groups. An asymmetric visible irradiation on one side of the PSS-PPy membrane induces a built-in electric field across the membrane due to the intrinsic photoelectronic property of PPy, which drives the cationic transport against the concentration gradient, demonstrating an ion-pumping effect. This work is a prototype that uses a geometry-symmetric conducting polymer membrane as a light-powered artificial ion pump for active ion transport, which exhibits potential applications in nanofluidic energy conversion.

Electrochemical reduction of nitrate in a catalytic carbon membrane nano-reactor.

Nitrate pollution is a critical environmental issue in need of urgent addressing. Electrochemical reduction is an attractive strategy for treating nitrate due to the environmental friendliness. However, it is still a challenge to achieve the simultaneous high activity and selectivity. Here we report the design of a porous tubular carbon membrane as the electrode deposited with catalysts, which provides a large triple-phase boundary area for nitrate removal reactions. The achieved nitrate removal rate is one order of magnitude higher than other literatures with high nitrate conversion and high selectivity of nitrogen. The carbon membrane itself had a limited catalytic property thus Cu-Pd bimetal catalysts were deposited inside the nano-pores to enhance the activity and selectivity. When Na2SO4 electrolyte was applied, the achieved single-pass removal of nitrate was increased from 55.15% (for blank membrane) to 97.12% by adding catalysts inside the membrane. In case of NaOH as the electrolyte, the single-pass nitrate removal efficiency, selectivity to nitrogen formation and nitrate removal rate was 90.66%, 96.40% and 1.47 × 10-3 mmol min-1 cm-2, respectively. Density functional theory studies demonstrate that the loading of bimetal catalysts compared with single metal catalysts enhances the adsorption of *NO3 on membrane surface favorable for N2 formation than NH3 on Cu-Pd surface. The application of catalytic carbon membrane nano-reactors can open new windows for nitrate removal due to the high reactor efficiency.

Kinetic Process of an Alkaline Earth Metal Ion Transmembrane through ZIF-8.

The confinement effect of biological ion channels regulates the transport of molecules and ions due to angstrom-sized pores. The structure of the potassium channel has a selection region (3-4 Å), a cavity (10 Å), and a gated region, while ZIF-8 has intrinsic pores with a 3.4 Å aperture and an 11.6 Å cavity similar to those of the potassium channel. Inspired by this, we constructed the glass/ZIF-8 hybrid membrane through an electrochemical growth process to explore the kinetics of the ion transmembrane by I-V curves and electrochemical impedance spectroscopy. These complementary approaches yield highly correlated results that show that ion transportation of the ZIF-8 membrane follows Arrhenius behavior. The rates of ions are controlled by the transmembrane activation energy, in which the ionic charge and radius play an important role.

Electrochromic Nanochannels for Visual Nanofluidic Manipulation in Integrated Ionic Circuits.

Nanochannel system provides a promising platform to create nanofluidic components in large-scale integrated circuits for "lab-on-a-chip" applications. However, it is a big challenge to achieve in situ monitoring on microscopic nanofluidic manipulation of single nanofluidic components in the integrated ionic circuit. Herein, we present a simple approach to realize visual nanofluidic manipulation in asymmetric nanochannels by the functionalization of an electrochromic polyaniline coating, which demonstrates redox-tunable surface charge accompanied by a visible color variation. The electrochromic nanochannels present a green color when behaving as ionic diodes, while the color turns to light yellow in a manner of ionic resistor. Moreover, both ionic transport behavior and color transition could respond well with alternating switch between redox states, contributing to a reversible and stable visual nanofluidic manipulation of electrochromic nanochannels. This work will create new avenues on in situ characterizing nanofluidic manipulation of nanofluidic components in integrated ionic circuits for intelligent sensing and detection applications.

An ionic diode based on a spontaneously formed polypyrrole-modified graphene oxide membrane.

Asymmetric membranes derived from the stacking of graphene oxide (GO) nanosheets have attracted great attention for the fabrication of ionic diodes. Herein, we described an ionic diode based on a polypyrrole-modified GO membrane with a vertical asymmetry, which was achieved by a spontaneous oxidation polymerization of pyrrole monomers on one side of the GO membrane in vapor phase. This asymmetric modification resulted in an asymmetric geometry due to the occupation of the interlayer space of one side of the GO membrane by polypyrrole. Our ionic diode demonstrated an obvious ionic rectification behavior over a wide voltage range. A calculation based on Poisson-Nernst-Planck equations was used to theoretically investigate the role of asymmetric modification of polypyrrole.

Rod-Cell-Mimetic Photochromic Layered Ion Channels with Multiple Switchable States for Controllable Ion Transport.

The controllable ion transport in the photoreceptors of rod cells is essentially important for the light detection and information transduction in visual systems. Herein, inspired by the photochromism-regulated ion transport in rod cells with stacking structure, layered ion channels have been developed with a visual photochromic function induced by the alternate irradiation with visible and UV light. The layered structure is formed by stacking spiropyran-modified montmorillonite 2D nanosheets on the surface of an alumina nanoporous membrane. The visual photochromism resulting from the photoisomerization of spiropyran chromophores reversibly regulates the ion transport through layered ion channels. Furthermore, the cooperation of photochromism and pH value achieves multiple switchable states of layered ion channels for the controllable ion transport mimicking the biological process of the visual cycle. The ion transport properties of these states are explained quantitatively by a theoretical calculation based on the Poisson and Nernst-Plank (PNP) equations.

A redox-generated biomimetic membrane potential across polypyrrole films.

Inspired by the formation mechanism of a biological membrane potential, we described the generation of an artificial membrane potential through redox-regulating anion distribution on the two sides of a polypyrrole film. The polarity of the membrane potential could be regulated by the redox reaction.

Layered photochromic films stacked from spiropyran-modified montmorillonite nanosheets.

Two-dimensional (2D) nanosheets are a class of fascinating host material that demonstrates a high specific surface area for the immobilization of functional molecules. Herein, we describe a layered photochromic film using montmorillonite 2D nanosheets immobilized with spiropyran units, which demonstrates a remarkable and reversible photochromic behavior. The synthesis of the layered photochromic film includes the intercalation and exfoliation of montmorillonite powders into 2D nanosheets using a spiropyran-modified surfactant and a subsequent vacuum filtration. The photochromic units of spiropyran-modified quaternary ammonium groups are immobilized on the surface of montmorillonite 2D nanosheets through an electrostatic interaction after exchanging with the native cations in montmorillonite during the intercalation and exfoliation. The photoisomerization of the spiropyran units between closed-ring spiropyran and open-ring merocyanine upon visible/UV irradiation contributes to the photochromic behavior of the layered film. The color contrast between the coloration and decoloration states of photochromic film is optimized by increasing the amount of spiropyran-modified cationic surfactant during the intercalation and exfoliation process. Our layered films with a visual photochromic behavior may promote their applications for optical data storage, optical switching and chemical sensing.

Anti-corrosion porous RuO2/NbC anodes for the electrochemical oxidation of phenol.

Efficient anode materials with porous structures have drawn increasing attention due to their high specific surface area, which can compensate for the slow reaction rate of electrochemical oxidation. However, the use of these materials is often limited due to their poor corrosion resistance. Herein, we report a facile scale-up method, by carbothermal reduction, for the preparation of porous niobium carbide to be used as an anode for the electrochemical oxidation of phenol in water. No niobium ions were detected when the anodes were under aggressive attack by sulfuric acid and under electrochemical corrosion tests with a current density less than 20.98 mA cm-2. The porous niobium carbide was further modified by applying a ruthenium oxide coating to improve its catalytic activity. The removal rates of phenol and chemical oxygen demand by the RuO2/NbC anode reached 1.87 × 10-2 mg min-1 cm-2 and 6.33 × 10-2 mg min-1 cm-2, respectively. The average current efficiency was 85.2%. Thus, an anti-corrosion, highly catalytically active and energy-efficient porous RuO2/NbC anode for the degradation of aqueous phenol in wastewater was successfully prepared.

Photosynthesis-inspired bifunctional energy-harvesting devices that convert light and salinity gradients into electricity.

Inspired by the bifunctional utilization of light energy and a proton gradient in photosynthesis, we proposed conceptually an energy-harvesting device that is capable of converting light and a salinity gradient into electricity simultaneously. Our bioinspired concept provided a potential opportunity to harvest multiple renewable energies and maximize the overall power output.

An electrochemical anodization strategy towards high-activity porous MoS2 electrodes for the hydrogen evolution reaction.

Molybdenum disulfide (MoS2) is a promising non-precious metal electrocatalyst for the hydrogen evolution reaction (HER). Herein, we have described an anodization route for the fabrication of porous MoS2 electrodes. The active porous MoS2 layer was directly formed on the surface of a Mo metal sheet when it was subjected to anodization in a sulfide-containing electrolyte. The Mo sheet served as both a supporter for MoS2 electrocatalysts and a conductive substrate for electron transport. After optimizing the anodization parameters, the anodized MoS2 electrode showed a high electrocatalytic activity with an onset potential of -0.18 V (vs. RHE) for the HER, a Tafel slope of ∼101 mV per decade and an overpotential of 0.23 V at a current density of 10 mA cm-2 for the HER. These results indicate that our facile anodization strategy is an efficient route towards a high-activity MoS2 electrode.