Accurate prediction of solvent flux in sub-1-nm slit-pore nanosheet membranes.

Nanosheet-based membranes have shown enormous potential for energy-efficient molecular transport and separation applications, but designing these membranes for specific separations remains a great challenge due to the lack of good understanding of fluid transport mechanisms in complex nanochannels. We synthesized reduced MXene/graphene hetero-channel membranes with sub-1-nm pores for experimental measurements and theoretical modeling of their structures and fluid transport rates. Our experiments showed that upon complete rejection of salt and organic dyes, these membranes with subnanometer channels exhibit remarkably high solvent fluxes, and their solvent transport behavior is very different from their homo-structured counterparts. We proposed a subcontinuum flow model that enables accurate prediction of solvent flux in sub-1-nm slit-pore membranes by building a direct relationship between the solvent molecule-channel wall interaction and flux from the confined physical properties of a liquid and the structural parameters of the membranes. This work provides a basis for the rational design of nanosheet-based membranes for advanced separation and emerging nanofluidics.

Novel D-π-A hemicyanine dye as photoinitiators for in situ hydrogel formation and DLP printing.

The field of biofabrication imposes stringent requirements on the polymerization activity and biosafety of photopolymeric hydrogel systems. In this investigation, we designed and synthesized four hemicyanine dyes with a D-π-A structure specifically tailored for biofabrication purposes. These novel dyes, incorporating carbazole (CZ), triphenylamine (TPA), anthracene (AN), and benzodithiophene (BDT) as electron donors, along with heterocyclic salt (IN) as electron acceptors, were prepared using a straightforward synthesis method. The absorption maxima of ANIN, CZIN, and TPAIN exceeded 500 nm, rendering them suitable co-initiators for the free radical photopolymerization of acrylates under green-red light exposure facilitated by light-emitting diodes (LEDs) and the co-initiator iodonium salt (ION). Notably, CZIN and TPAIN, due to their robust dye absorption and efficient electron transfer to ION, functioned as high-performance photosensitizers. Meanwhile, BDTIN, with its strong and broad absorption range (400-600 nm), enhanced the accuracy of visible light photopolymerization. These dyes exhibit characteristics such as facile synthesis, heightened photo stability, and non-toxicity and also demonstrate the ability to discern the alkalinity of a solution to some extent. Furthermore, we explored the application of these hemicyanine dyes in 3D printing, showing potential to enhance printing resolution in DLP 3D printing (digital light process 3D printing).

Reversible pH-Gated MXene Membranes with Ultrahigh Mono-/Divalent-Ion Selectivity.

Artificial ion channel membranes hold high promise in water treatment, nanofluidics, and energy conversion, but it remains a great challenge to construct such smart membranes with both reversible ion-gating capability and desirable ion selectivity. Herein, we constructed a smart MXene-based membrane via p-phenylenediamine functionalization (MLM-PPD) with highly stable and aligned two-dimensional subnanochannels, which exhibits reversible ion-gating capability and ultrahigh metal ion selectivity similar to biological ion channels. The pH-sensitive groups within the MLM-PPD channel confers excellent reversible Mg2+-gating capability with a pH-switching ratio of up to 100. The mono/divalent metal-ion selectivity up to 1243.8 and 400.9 for K+/Mg2+ and Li+/Mg2+, respectively, outperforms other reported membranes. Theoretical calculations combined with experimental results reveal that the steric hindrance and stronger PPD-ion interactions substantially enhance the energy barrier for divalent metal ions passing through the MLM-PPD, and thus leading to ultrahigh mono/divalent metal-ion selectivity. This work provides a new strategy for developing artificial-ion channel membranes with both reversible ion-gating functionality and high-ion selectivity for various applications.

Electricity generation from carbon dioxide adsorption by spatially nanoconfined ion separation.

Selective ion transport underpins fundamental biological processes for efficient energy conversion and signal propagation. Mimicking these 'ionics' in synthetic nanofluidic channels has been increasingly promising for realizing self-sustained systems by harvesting clean energy from diverse environments, such as light, moisture, salinity gradient, etc. Here, we report a spatially nanoconfined ion separation strategy that enables harvesting electricity from CO2 adsorption. This breakthrough relies on the development of Nanosheet-Agarose Hydrogel (NAH) composite-based generators, wherein the oppositely charged ions are released in water-filled hydrogel channels upon adsorbing CO2. By tuning the ion size and ion-channel interactions, the released cations at the hundred-nanometer scale are spatially confined within the hydrogel network, while ångström-scale anions pass through unhindered. This leads to near-perfect anion/cation separation across the generator with a selectivity (D-/D+) of up to 1.8 × 106, allowing conversion into external electricity. With amplification by connecting multiple as-designed generators, the ion separation-induced electricity reaching 5 V is used to power electronic devices. This study introduces an effective spatial nanoconfinement strategy for widely demanded high-precision ion separation, encouraging a carbon-negative technique with simultaneous CO2 adsorption and energy generation.

Understanding the Electrochemical Extraction of Lithium from Ultradilute Solutions.

The electrochemical extraction of lithium (Li) from aqueous sources using electrochemical means is a promising direct Li extraction technology. However, to this date, most electrochemical Li extraction studies are confined to Li-rich brine, neglecting the practical and existing Li-lean resources, with their overall extraction behaviors currently not fully understood. More still, the effect of elevated sodium (Na) concentrations typically found in most Li-lean water sources on Li extraction is unclear. Hence, in this work, we first understand the electrochemical Li extraction behaviors from ultradilute solutions using spinel lithium manganese oxide as the model electrode. We discovered that Li extraction depends highly on the Li concentration and cell operation current density. Then, we switched our focus on low Li to Na ratio solutions, revealing that Na can dominate the electrostatic screening layer, reducing Li ion concentration. Based on these understandings, we rationally employed pulsed electrochemical operation to restructure the electrode surface and distribute the surface-adsorbed species, which efficiently achieves a high Li selectivity even in extremely low initial Li/Na concentrations of up to 1:20,000.

Two-dimensional MXene membranes with biomimetic sub-nanochannels for enhanced cation sieving.

Membranes with high ion permeability and selectivity are of considerable interest for sustainable water treatment, resource extraction and energy storage. Herein, inspired by K+ channel of streptomyces A (KcsA K+), we have constructed cation sieving membranes using MXene nanosheets and Ethylenediaminetetraacetic acid (EDTA) molecules as building blocks. Numerous negatively charged oxygen atoms of EDTA molecules and 6.0 Å two-dimensional (2D) sub-nanochannel of MXene nanosheets enable biomimetic channel size, chemical groups and tunable charge density for the resulting membranes. The membranes show the capability to recognize monovalent/divalent cations, achieving excellent K+/Mg2+ selectivity of 121.2 using mixed salt solution as the feed, which outperforms other reported membranes under similar testing conditions and transcends the current upper limit. Characterization and simulations indicate that the cation recognition effect of EDTA and partial dehydration effects play critical roles in cations selective sieving and increasing the local charge density within the sub-nanochannel significantly improves cation selectivity. Our findings provide a theoretical basis for ions transport in sub-nanochannels and an alternative strategy for design ions separation membranes.

Nanoconfinement enabled non-covalently decorated MXene membranes for ion-sieving.

Covalent modification is commonly used to tune the channel size and functionality of 2D membranes. However, common synthesis strategies used to produce such modifications are known to disrupt the structure of the membranes. Herein, we report less intrusive yet equally effective non-covalent modifications on Ti3C2Tx MXene membranes by a solvent treatment, where the channels are robustly decorated by protic solvents via hydrogen bond network. The densely functionalized (-O, -F, -OH) Ti3C2Tx channel allows multiple hydrogen bond establishment and its sub-1-nm size induces a nanoconfinement effect to greatly strengthen these interactions by maintaining solvent-MXene distance and solvent orientation. In sub-1-nm ion sieving and separation, as-decorated membranes exhibit stable ion rejection, and proton-cation (H+/Mn+) selectivity that is up to 50 times and 30 times, respectively, higher than that of pristine membranes. It demonstrates the feasibility of non-covalent methods as a broad modification alternative for nanochannels integrated in energy-, resource- and environment-related applications.

Dehydration-enhanced ion-pore interactions dominate anion transport and selectivity in nanochannels.

State-of-the-art ion-selective membranes with ultrahigh precision are of significance for water desalination and energy conservation, but their development is limited by the lack of understanding of the mechanisms of ion transport at the subnanometer scale. Herein, we investigate transport of three typical anions (F-, Cl-, and Br-) under confinement using in situ liquid time-of-flight secondary ion mass spectrometry in combination with transition-state theory. The operando analysis reveals that dehydration and related ion-pore interactions govern anion-selective transport. For strongly hydrated ions [(H2O)nF- and (H2O)nCl-], dehydration enhances ion effective charge and thus the electrostatic interactions with membrane, observed as an increase in decomposed energy from electrostatics, leading to more hindered transport. Contrarily, weakly hydrated ions [(H2O)nBr-] have greater permeability as they allow an intact hydration structure during transport due to their smaller size and the most right-skewed hydration distribution. Our work demonstrates that precisely regulating ion dehydration to maximize the difference in ion-pore interactions could enable the development of ideal ion-selective membranes.

Smart utilisation of reverse solute diffusion in forward osmosis for water treatment: A mini review.

Forward osmosis (FO) has been widely studied as a promising technology in wastewater treatment, but undesirable reverse solute diffusion (RSD) is inevitable in the FO process. The RSD is generally regarded as a negative factor for the FO process, resulting in the loss of draw solutes and reduced FO efficiency. Conventional strategies to address RSD focus on reducing the amount of reverse draw solutes by fabricating high selective FO membranes and/or selecting the draw solute with low diffusion. However, since RSD is inevitable, doubts have been raised about the strategies to cope with the already occurring reverse draw solutes in the feed solution, and the feasibility to positively utilise the RSD phenomenon to improve the FO process. Herein, we review the state-of-the-art applications of RSD and their benefits such as improving selectivity and maintaining the stability of the feed solution for both independent FO processes and FO integrated processes. We also provide an outlook and discuss important considerations, including membrane fouling, membrane development and draw/feed solution properties, in RSD utilisation for water and wastewater treatment.

Scalable high yield exfoliation for monolayer nanosheets.

Although two-dimensional (2D) materials have grown into an extended family that accommodates hundreds of members and have demonstrated promising advantages in many fields, their practical applications are still hindered by the lack of scalable high-yield production of monolayer products. Here, we show that scalable production of monolayer nanosheets can be achieved by a facile ball-milling exfoliation method with the assistance of viscous polyethyleneimine (PEI) liquid. As a demonstration, graphite is effectively exfoliated into graphene nanosheets, achieving a high monolayer percentage of 97.9% at a yield of 78.3%. The universality of this technique is also proven by successfully exfoliating other types of representative layered materials with different structures, such as carbon nitride, covalent organic framework, zeolitic imidazolate framework and hexagonal boron nitride. This scalable exfoliation technique for monolayer nanosheets could catalyze the synthesis and industrialization of 2D nanosheet materials.

Photo-electrochemical oxidation herbicides removal in stormwater: Degradation mechanism and pathway investigation.

Although advanced oxidation processes (AOPs) such as photoelectrochemical oxidation (PECO), electrochemical oxidation (ECO) and photocatalytic oxidation (PCO), have shown potential for wastewater treatment, their application in urban stormwater has rarely been studied. This paper explored their major degradation mechanisms and possible degradation pathways of herbicides for stormwater applications (with treatment difficulty compared with wastewater). PECO and ECO showed excellent removal performance for diuron (100 %) and moderate for atrazine (around 35 %) under a relatively low potential (2 V). Superoxide radical (·O2-) has been found to be the dominant reactive species. Besides, there is evidence to indicate that hydroxyl radical (·OH) and free chlorine (·Cl) also support the degradation reactions. Up to 11 possible intermediate products have been identified during both diuron and atrazine degradation processes under PECO operation. Based on the proposed possible degradation pathways, the intermediates presented during PECO are species with further oxidation. As evidenced by the undetected species of more oxidized intermediates for ECO and PCO, some further degradation steps are missing, which demonstrate their lower oxidation capacity leading to incomplete decomposition of stormwater herbicides. Thus, PECO has a great potential to be developed into a passive stormwater degradation system due to its strong oxidation potential.

Novel Poly(ester amide) Membranes with Tunable Crosslinked Structures for Nanofiltration.

Tuning the crosslinking density of interfacial-polymerized nanofiltration (NF) membranes varying from loose to dense structures can make them meet the demand of various applications. The properties (e.g., pore size and porosity) of NF membranes can be tuned by choosing monomers with different structures and reactivities. Herein, tris(hydroxymethyl)aminomethane (THAM), a low-cost and green monomer, is first employed for the preparation of poly(ester amide) (PEA) thin-film composite membranes via interfacial polymerization. The moderate reactivity of THAM enables rational regulation of the crosslinking density of PEA membranes from loose to dense structures by varying the THAM concentration, which can hardly be achieved for traditional polyamide or polyester membranes. The developed PEA membranes with a wide tunability range of crosslinking densities broaden their potential utility in NF. PEA membranes with dense structures show exceptional desalination performance with a water permeance of 11.1 L m-2 h-1 bar-1 and a Na2SO4 rejection of 97.1%. However, loose PEA membranes exhibit good dye/salt separation performance with a dye removal rate over 95.0% and negligible NaCl rejection (<7.5%), as well as high water permeance (>45 L m-2 h-1 bar-1). This work implies that PEA membranes with tunable crosslinked structures provide new possibilities for the development of task-specific separation membranes.

Monodispersed CuO nanoparticles supported on mineral substrates for groundwater remediation via a nonradical pathway.

Nonradical oxidation based on singlet oxygen (1O2) has attracted great interest in groundwater remediation due to the selective oxidation property and good resistance to background constituents. Herein, recoverable CuO nanoparticles (NPs) supported on mineral substrates (SiO2) were prepared by calcination of surface-coated metal-plant phenolic networks and explored for peroxymonosulfate (PMS) activation to generate 1O2 for degrading organic pollutants in groundwater. CuO NPs with a close particle size (40 nm) were spatially monodispersed on SiO2 substrates, allowing highly exposure of active sites and consequently leading to outstanding catalytic performance. Efficient removal of various organic pollutants was obtained by the supported CuO NPs/PMS system under wide operation conditions, e.g., working pH, background anions and natural organic matters. Chemical scavenging experiments, electron paramagnetic resonance tests, furfuryl alcohol decay and solvent dependency experiments confirmed the formation of 1O2 and its dominant role in pollutants removal. In situ characterization with ATR-FTIR and Raman spectroscopy and computational calculation revealed that a redox cycle of surface Cu(II)-Cu(III)-Cu(II) was responsible for the generation of 1O2. The feasibility of the supported CuO NPs/PMS for actual groundwater remediation was evaluated via a flow-through test in a fixed-bed column, which manifested long-term durability, high mineralization ratio and low metal ion leaching.

Oriented UiO-67 Metal-Organic Framework Membrane with Fast and Selective Lithium-Ion Transport.

Metal-organic frameworks (MOFs) membranes with high pore density and tunable pore size down to the subnanoscale exhibit great potential in ion separation when appropriately designed and prepared. By a washing-assisted secondary growing method, a well intergrown UiO-67 membrane with preferential growth along the [022] direction was synthesized on a polyvinylpyrrolidone (PVP)-modified AAO substrate. Because of the oriented growth of UiO-67 nanocrystals, highly interconnected ion-transporting channels are created throughout the UiO-67/AAO membrane capable of achieving an ultrahigh Li+ permeance of 27.01 mol m-2 h-1 as well as very decent Li+ /Mg2+ selectivity of up to 159.4. Molecular dynamics simulations reveal that the high selectivity is associated with the large disparity of the transport energy barrier between Li+ and Mg2+ , which is caused by different extents of ion dehydration in unique bimodal and oriented membrane channels.

Insight into the Reactivity of Carbon Structures for Nitrogen Reduction Reaction.

Graphene-based structures have been widely reported as promising metal-free catalysts for nitrogen reduction reaction. To explain the reactivity origin, various structures have been proposed and debated, including defects, functional groups, and doped heteroatoms. This computational work demonstrates that these structures may evolve from one to another under electrochemical conditions, generating weakly coordinated carbons, which have been identified as the active sites for N2 adsorption and activation.

Stormwater herbicides removal with a solar-driven advanced oxidation process: A feasibility investigation.

The solar driven advanced oxidation process (AOP) has the potential to be developed as a passive stormwater post-treatment method. Despite its widespread studies in wastewater treatment, the applicability of the process for micropollutant removal in stormwater (which has very different chemical properties from wastewater) is still unknown. This paper investigated the feasibility of three different AOP processes for the degradation of two herbicides (diuron and atrazine) in pre-treated stormwater: (i) photoelectrochemical oxidation (PECO), (ii) electrochemical oxidation (ECO), and (iii) photocatalytic oxidation (PCO). The durability of different anode materials, the effects of catalyst loading, and solar photo- and thermal impacts under different applied voltages were studied. Boron-doped diamond (BDD) was found to be the most durable anode material compared to carbon fiber and titanium foil for long-term operation. Due to the very low electroconductivity of stormwater, a high voltage was required, causing severe oxidation of the carbon fiber material. PECO achieved the best degradation results compared to ECO and PCO, with over 90% degradation of both herbicides in 2 h under 5 V, following a first-order decay process (with a half-life value of 0.40 h for diuron and 0.58 h for atrazine). The voltage increase had a positive impact on the oxidation processes, with 5 V found to be the optimal applied voltage, while catalyst loading had a negligible effect. Interestingly, the solar thermal effect plays a dominant role in enhancing the performance of the PECO process, which indicates the potential of integrating a photovoltaic chamber with a PECO system to harness both the light and heat of solar energy for stormwater treatment.

The removal mechanism of nitrobenzene by the Cu-Fe/Carbon material under different aeration conditions.

Zero-valent Cu-Fe bimetallic porous carbon materials were successfully applied to remediate organic wastewater. In this work, we successfully recycled the layered double hydroxides (LDHs) adsorbed with Orange II (OII) to form a zero-valent Cu-Fe bimetallic porous carbon material (CuFe/Carbon). The characterization results showed that CuFe/Carbon was a zero-valent Cu-Fe bimetallic porous graphene-like carbon material. In the course of the experiment, we found that aeration condition had a great influence on the activity of CuFe/Carbon. The removal efficiency of nitrobenzene (NB) was 100 % in nitrogen system and 48 % in air system. The active species of O2- and OH was formed under air condition, while there was no active species under nitrogen condition. NB was reduced to aniline directly under nitrogen condition. We proposed there were reduction and oxidation mechanisms under different aeration conditions. This work mainly investigated the conversion process of a novel material under different reaction conditions, which provided theoretical support for the removal of organic matters.

Synergistic effect of dual sites on bimetal-organic frameworks for highly efficient peroxide activation.

Active site engineering is of significant importance for developing high activity metal-organic frameworks (MOFs) for catalytic applications. Herein, we develop a one-pot strategy to construct bimetal organic frameworks with Fe-Co dual sites for Fenton-like catalysis. Density functional theory (DFT) demonstrated that the introducing Co heteroatoms into MIL-101(Fe) (MIL represents Matérial Institute Lavoisier) was favorable for the formation of electron-deficient centers around benzene rings and electron-rich centers around Fe/Co. This synergistic effect could effectively decrease the energy barrier of H2O2 activation. Due to the facilitated charge transfer in the coordinated structures, MIL-101(Fe,Co) with engineered dual sites exhibited exceptionally high efficiency for the degradation of ciprofloxacin (CIP). The reaction rate of MIL-101(Fe,Co)/H2O2 system was 0.12 min-1, which was nearly 7.5 times higher than that of pristine MIL-101(Fe). The reaction mechanism of heterogeneous Fenton-like catalysis was fundamentally investigated by series of in-situ techniques, such as DRIFTS and Raman. ·OH radicals generated by H2O2 activation endowed the inspiring ability of MIL-101(Fe,Co) for water decontamination. This work offers a facile principle of exploring MOFs-based Fenton-like catalysts with a wide working pH range for environmental applications.

Carbon-based materials for photo- and electrocatalytic synthesis of hydrogen peroxide.

The high demand for hydrogen peroxide (H2O2) has been dominantly supplied by the anthraquinone process for various applications globally, including chemical synthesis and wastewater treatment. However, the centralized manufacturing and intensive energy input and waste output are significant challenges associated with this process. Accordingly, the on-site production of H2O2via electro- and photocatalytic water oxidation and oxygen reduction partially is greener and easier to handle and has recently emerged with extensive research aiming to seek active, selective and stable catalysts. Herein, we review the current status and future perspectives in this field focused on carbon-based catalysts and their hybrids, since they are relatively inexpensive, bio-friendly and flexible for structural modulation. We present state-of-the-art progress, typical strategies for catalyst engineering towards selective and active H2O2 production, discussion on electro- and photochemical mechanisms and H2O2 formation through both reductive and oxidative reaction pathways, and conclude with the key challenges to be overcome. We expect promising developments would be inspired in the near future towards practical decentralized H2O2 production and its direct use.

Selective Permeation of Water through Angstrom-Channel Graphene Membranes for Bioethanol Concentration.

Graphene-based laminate membranes have been theoretically predicted to selectively transport ethanol from ethanol-water solution while blocking water. Here, robust angstrom-channel graphene membranes (ACGMs) fabricated by intercalating carbon sheets derived from chitosan into thermally reduced graphene oxide (GO) sheets are reported. ACGMs with robust and continuous slit-shaped pores (an average pore size of 3.9 Å) are investigated for the dehydration of ethanol. Surprisingly, only water permeates through ACGMs in the presence of aqueous ethanol solution. For the water-ethanol mixture containing 90 wt% ethanol, water can selectively permeate through ACGMs with a water flux of 63.8 ± 3.2 kg m-2 h-1 at 20 °C and 389.1 ± 19.4 kg m-2 h-1 at 60 °C, which are over two orders of magnitude higher than those of conventional pervaporation membranes. This means that ACGMs can effectively operate at room temperature. Moreover, the ethanol can be fast concentrated to high purity (up to 99.9 wt%). Therefore, ACGMs are very promising for production of bioethanol with high efficiency, thus improving its process sustainability.