Ultrathin 2D Research Articles

High-Performance Ultra-Broadband Photodetector Based on Fe3O4/CrSiTe3 Heterostructures.

Photodetectors based on advanced materials with a broad spectral photoresponse, high sensitivity, huge integration ability, room-temperature operation, and stable environmental stability are highly desired for diversified applications of imaging, sensing, and communication. Herein, a high-performance ultra-broadband photodetector based on an ultrathin two-dimensional (2D) Fe3O4 nanoflake heterostructure with high sensitivity was designed. The photodetector response light was from visible 405 nm to long-wave infrared (LWIR) 10.6 μm in ambient air. The competitive performances, including a high photoresponsivity (R) of 182.8 A W-1, fast speed with the rise time τr = 8.8 μs, and decay time τd = 4.1 μs, were demonstrated in the visible range. Notably, the device exhibits an excellent uncooled LWIR detection ability, with a high R of 1.4 A W-1 realized at a 1.5 V bias. In the full spectral range, the noise equivalent power is lower than 0.79 pW Hz-1/2, and specific detectivity (D*) is higher than 4.9 × 108 cm Hz1/2 W-1 in ambient air. This work provides alternative ultrathin 2D materials for future infrared optoelectronic devices.

Monodispersed Cu sites assembled on ultrathin 2D C3N4 for efficient electrocatalytic CO2 methanation

Electrocatalytic CO2 reduction (ECO2R) to methane is a promising technology that could effectively realize carbon resource integration and energy recycling. Currently, Cu-based catalysts are the most effective catalysts for this process, and a long-term goal of high selectivity and high stability still remains elusive. In this study, a controllable and multistep solid-state pyrolysis route is implemented to successfully introduce atomically dispersed Cu sites (Cu SA) into the two-dimensional carbon nitride (2D C3N4) matrices. The active site density and morphology structure of the Cu SA-2D C3N4 catalyst could be precisely controlled by adjusting the calcination process. Through the strategic combination of an ultrathin 2D structure and uniformly dispersed active sites, the Cu SA-2D C3N4 maximizes the exposure of active sites while suppressing competitive C–C coupling reactions. Ultimately, the optimized Cu SA-2D C3N4-30 exhibit a Faradaic efficiency of 62.9 % for CO2-to-CH4 conversion with a partial current density of 172.4 mA cm−2 at -1.68 V vs. RHE. This work demonstrates an advanced Cu-based electrocatalyst that effectively improves the performance of electrocatalytic CO2 methanation.

Above-room-temperature intrinsic ferromagnetism in ultrathin van der Waals crystal Fe3+xGaTe2

Two-dimensional (2D) van der Waals (vdW) magnets are crucial for ultra-compact spintronics. However, so far, no vdW crystal has exhibited tunable above-room-temperature intrinsic ferromagnetism in the 2D ultrathin regime. Here, we report the tunable above-room-temperature intrinsic ferromagnetism in ultrathin vdW crystal Fe3+xGaTe2 (x = 0 and 0.3). By increasing the Fe content, the Curie temperature (TC) and room-temperature saturation magnetization of bulk Fe3+xGaTe2 crystals are enhanced from 354 to 376 K and 43.9 to 50.4 emu·g−1, respectively. Remarkably, the robust anomalous Hall effect in 3-nm Fe3.3GaTe2 indicates a record-high TC of 340 K and a large room-temperature perpendicular magnetic anisotropy energy of 6.6 × 105 J m−3, superior to other ultrathin vdW ferromagnets. First-principles calculations reveal the asymmetric density of states and an additional large spin exchange interaction in ultrathin Fe3+xGaTe2 responsible for robust intrinsic ferromagnetism and higher TC. This work opens a window for above-room-temperature ultrathin 2D magnets in vdW-integrated spintronics.

Ultrathin 2D[sbnd]2D WO3-x-C3N4 heterostructure-based high-efficiency photocatalyst for selective oxidation of toluene

Photocatalytic oxidation of toluene for the organic synthesis of value-added benzaldehyde has attracted great attention in recent years. However, activation of CH bonds and selective production of benzaldehyde under mild green conditions remains a great challenge. Herein, a series of two-dimensional (2D) ultrathin heterostructure-based components (WO3-x-C3N4 nanosheets), fabricated by coupling oxygen-deficient WO3-x with amorphous C3N4 via a simple electrostatic self-assembly method, was demonstrated as high-efficiency photocatalysts to produce benzaldehyde in the presence O2 as oxidant at room temperature. Under optimal conditions, the prepared 10WCN sample (10 wt% WO3-x-C3N4) exhibited improved photocatalytic oxidation ability with a good benzaldehyde selectivity (96 %) and high benzaldehyde yield (2738.6 μmol g−1 h−1) within 6 h, which is 6.6 and 3.3 times than that of pure WO3-x (412.5 μmol g−1 h−1) and C3N4 (835.7 μmol g−1 h−1). The enhanced photocatalytic performance was due to the constructed 2D type II heterojunction and abundant oxygen vacancies (OVs), contributing to the photoinduced carriers' separation and migration efficiently. This work indicates the synergistic effect of defect metal oxides and 2D ultrathin sheet-to-sheet heterojunctions in photocatalytic hydrocarbon conversion.

Modulation of π-Electron Density in Ultrathin 2D Layers of Graphite Carbon Nitride for Efficient Photocatalytic Hydrogen Production.

The rational design and synthesis of novel semiconductor nano-/quantum materials have been ambitiously pursued in the field of photocatalysis as the technology is promising and critical for attaining future energy and environmental sustainability. Herein, the integrity of aromatic carbon into graphitic carbon nitride (CN) at the same molecular plane with a few 2D layers is achieved by using modulated precursors of CN, forming carbon regulated ultrathin CN (CUCN) with improved charge transfer kinetics and photocatalytic hydrogen production. The grafted graphite rings adjacent to carbon nitride frameworks induce a significant rearrangement and relocalization of the overall framework, and form conjugated sp2 hybridized interfaces and internal electric fields that drive the separation and directional transfer of photogenerated electrons from CN sheets towards intralayer graphite regions, where the photocatalytic hydrogen evolution reaction occurs extensively, yielding largely increased HER rate of 2231.8 µmol g-1 h-1 by 8.2 times relative to CN, as well as a remarkable apparent quantum yield of 2.93% under monochromatic light at 420 nm. The high physicochemical stability and low synthesis cost of CUCN make it a potential benchmark photocatalyst that can be readily modified via element doping, heterojunction introduction, defect engineering, and so on, to further enhance its HER performance.

Liquid–liquid interface‐assisted growth of two‐dimensional organic semiconductor single crystals: Mechanisms, properties, and applications

AbstractTwo‐dimensional organic semiconductor single crystals (2D OSSCs) represent the promising candidates for the construction of high‐performance electronic and optoelectronic devices due to their ultrathin thicknesses, free of grain boundaries, and long‐range ordered molecular structures. In recent years, substantial efforts have been devoted to the fabrication of the large‐sized and layer‐controlled 2D OSSCs at the liquid‐liquid interface. This unique interface could act as the molecular flat and defect‐free substrate for regulating the nucleation and growth processes and enabling the formation of large‐sized ultrathin 2D OSSCs. Therefore, this review focuses on the liquid–liquid interface‐assisted growth methods for the controllable preparation of 2D OSSCs, with a particular emphasis on the advantages and limitations of the corresponding methods. Furthermore, the typical methods employed to control the crystal sizes, morphologies, structures, and orientations of 2D OSSCs at the liquid–liquid interface are discussed in detail. Then, the recent progresses on the 2D OSSCs‐based optoelectronic devices, such as organic field‐effect transistors, ambipolar transistors, and phototransistors are highlighted. Finally, the key challenges and further outlook are proposed in order to promote the future development of the 2D OSSCs in the field of the next‐generation organic optoelectronic devices.

Emerging chiral two-dimensional materials.

Research into 2D materials has been growing with impressive speed since the discovery of graphene. Such layered materials with ultrathin morphologies and extreme aspect ratios currently display a vast range of properties; however, until recently a conspicuously missing property of 2D materials was global chirality. The situation has changed over the past few years with the implementation of several distinct types of ultrathin chiral 2D crystals. Here we offer a forward-looking perspective on this field to comprehend the fundamentals of global chirality in two dimensions and develop new directions. We specifically discuss the experimental achievements of the emerging chiral 2D materials with a focus on their design strategy, synthesis, structural characterization, fundamental physical properties and possible applications. We will highlight how the molecular-scale local chirality could be significantly transmitted and amplified throughout ultrathin single-crystalline 2D structures, resulting in distinctive global chirality that brings more sophisticated functions.

Boosting acidic hydrogen peroxide electrosynthesis on 2D metal-organic framework nanosheets based on cobalt porphyrins

The 2-electron electrocatalytic oxygen reduction reaction (2e− ORR) to hydrogen peroxide (H2O2) represents a promising strategy to resolve the high energy consumption and increasing environmental concerns inherent in the traditional anthraquinone process. The acidic 2e− ORR has emerged as an exciting alternative for industrial-level H2O2 production, whereas is hampered by the inferior H2O2 selectivity due to the uncontrollable proton-coupled electron transfer processes in an acidic environment. Herein, an ultrathin 2D metal–organic frameworks (MOFs) nanosheet based on cobalt tetra(4-carboxyphenyl) porphine (Co-TCPP NSs) is designed to promote H2O2 selectivity up to 96.5 %, accompanied with a remarkable H2O2 generation rate of 4677.42 mg·L−1·h−1. Of note, the Co-TCPP NSs also demonstrate its potential for the electro-Fenton process with a cumulative H2O2 concentration of 1.21 wt%, highlighting its practical potential in portable H2O2 generation electrochemical devices for distributed applications. Our findings demonstrated that the efficient H2O2 electrosynthesis could be attributed to the attenuated *OOH adsorption over Co-N4 moiety on the Co-TCPP NSs, which consequently suppresses its further reduction to form H2O. This work highlights the potential of 2D MOF architecture for the 2e− ORR and provides an atomic-level insight into the enhanced H2O2 selectivity.

Hydrothermal-based controllable synthesis and structural-optical characterization of 2D-MoS2/graphene nanocomposites for optoelectronic applications

This study presents a two-dimensional (2D) nanocomposite of molybdenum disulfide/graphene (2D-MoS2/C) synthesized via a hydrothermal method at 230 °C for 2 h. Comprehensive characterization using XRD, FESEM, HRTEM, Raman spectroscopy, XPS, UV–Vis spectroscopy, and PL measurements revealed detailed microstructural, morphological, compositional, and optical properties. FESEM confirmed the uniform crystallization of ultrathin 2D MoS2 nanocrystals on graphene sheets, while TEM and HRTEM showed vertical growth of 2D MoS2 nanosheets (∼3–6 nm thick), forming a 2D MoS2/C architecture. XRD and Raman analyses verified the hexagonal 2H–MoS2 phase with minimal impurities, supported by XPS measurement. MicroRaman analysis indicated defect repair in graphene oxide substrate, evidenced by reduced D-band intensity and an enhanced 2D-band. The 2D MoS2/C nanocomposite exhibited significant photoluminescence with distinct emission peaks in the visible range (∼1.75–2.05 eV), surpassing the 2D MoS2 counterpart. Notably, 2D MoS2/C thin films showed high absorbance (∼83 %) compared to graphene oxide (∼48.4 %) and bare 2D MoS2 (∼22.1 %), highlighting enhanced light-matter interaction. This straightforward, cost-effective synthesis approach offers promising potential for MoS2/C nanocomposite applications in optoelectronics and catalysis.

Highly Efficient, Flexible, and Self-Healable Moisture-Driven Energy Harvester Based on 2D Vanadium Pentoxide Nanosheets

The ubiquitous source of atmospheric moisture brought about a fascinating research avenue of extracting atmospheric water to generate sustainable electricity. Energy may be extracted from ambient moisture with obvious and substantial advantages. This point-of-use technology provides a decentralized alternative to meet the energy needs in isolated off-grid places. Unlike traditional energy generators which predominantly rely upon fossil fuel, moisture-induced energy generators can extract energy from moisture in a sustainable and eco-friendly way. Herein, we demonstrated a self-healable moist electric generator (MEG) based on vanadium pentoxide (V2O5) 2D nanosheet membranes. Lamellar membranes of V2O5 nanosheets have been shown to be excellent cation conductors and excellent materials for harvesting energy from ambient moisture. Ultra-thin 2D nanosheets of V2O5 was obtained by treatment of bulk V2O5 crystals with hydrogen peroxide. V2O5 nanosheet membrane was fabricated by vacuum-assisted filtration of 2D V2O5 nanosheets dispersion over a PTFE support membrane. The V2O5 membrane was easily peeled off from the support membrane on drying to obtain a flexible and freestanding V2O5 membrane. The V2O5 membrane consisting of percolated nanofluidic channels was sandwiched between a bottom solid copper foil and a perforated copper foil as the bottom electrode. The top electrode is perforated for exposure to atmospheric humidity. As the atmospheric water molecules come in contact with the V2O5 surface, an open-circuit voltage of 0.5 Volts and a short-circuit current of 0.3 microamperes is generated. The generated voltage and current is attributed to the preferential flow of cations through the V2O5 nanochannels. The exposed surface and edges of V2O5 nanosheets have a high negative surface charge which results in the splitting of water molecules into H3O+ and OH- ions. An electrical double layer (EDL) is established at the V2O5/water interface which selectively permits H3O+ ions through the channels. The mobile ions of the EDL transport through the nanofluidic channels creating a gradient between the two electrodes, resulting in a constant potential difference between the top and bottom electrodes which is harvested as electric current. The MEGs can be easily connected in parallel or series to enhance the current and voltage respectively. We demonstrate ten MEGs connected in series to power small electronic devices such as calculators and humidity meters. One of the key features of the V2O5 MEG is its ability to repair any physical damage to the active material owing to the water-assisted healing characteristics V2O5 membrane. Figure 1

Decorating Cage-Shaped Cavities with Carboxyl Groups on Two-Dimensional MOF Nanosheet for Trace Uranium(VI) Trapping.

The efficient and complete extraction of uranium from aqueous solutions is crucial for safeguarding human health from potential radiotoxicity and chemotoxicity. Herein, an ultrathin 2D metal-organic framework (MOF) nanosheet with cavity structures was elaborately constructed, based on a calix[4]arene ligand. The large molecular skeleton and cup-shaped feature of the calix[4]arene enabled the as-prepared MOFs with large layer separations, which can be readily delaminated into ultrathin single-layer (∼1.25 nm) nanosheets. The incorporation of permanent cavity structures to the MOF nanosheets can fully utilize their structural features of readily accessible adsorption groups and exposed surface area in uranium removal, reaching ultrafast adsorption kinetics; the functionalized cavity structure endowed MOF nanosheets with the ability to preconcentrate and extract uranium from aqueous solutions with ultrahigh efficiencies, even at extremely low concentrations. As a result, relatively high removal ratios (>95%) can be achieved for uranium within 5 min, even in the ultralow concentration range of 75-250 ppb, and the residual uranium was reduced to below 4.9 ppb. The MOF nanosheets also exhibited extremely high anti-interference ability, which could efficiently remove the low-level uranium (∼150 ppb) from various real samples. The characterizations and density functional theory calculations demonstrated that the synergistic effects of multiple interactions between the carboxylate groups and cage-like cavities with uranyl ions can be responsible for the efficient and selective uranium extraction.

Ligand Tail Controls the Conformation of Indium Sulfide Ultrathin Nanoribbons.

We report the conformational control of 2D ultrathin indium sulfide nanoribbons by tuning their amine ligands' alkyl chain. The initial orthorhombic InS nanoribbons bare n-octylamine ligands and display a highly curved geometry with a characteristic figure of eight shapes. Exchanging the native ligand by oleylamine induces their complete unfolding to yield flat board-shaped nanoribbons. Significant strain variations in the InS crystal structure accompany this shape-shifting. By tuning the linear alkyl chain length from 4 to 18 carbon atoms, we show using small-angle X-ray scattering in solution and transmission electron microscopy that the curvature of the nanoribbon subtly depends on the ligand-ligand interactions at the nanoribbon's surface. The curvature decreases gradually as the chain length increases, while carbon unsaturation has an unexpectedly significant effect at constant chain length. These experiments shed light on the critical role of the ligand monolayer on the curvature of ultrathin 2D crystalline nanosheets and demonstrate that weak supramolecular forces within the organic part of colloidal nanocrystals can dramatically impact their shape. This transduction mechanism, in which changes in the organic monolayer impact the shape of a nanocrystal, will help to devise new strategies to design stimuli-responsive systems that take advantage of both the flexibility of organic moieties and the physical properties of the inorganic core.

Ultra-Wide Interlayered WxMo2xSy Alloy Electrode Patterning through High-Precision Controllable Photonic-Synthesis.

Ultra-thin 2D materials have great potential as electrodes for micro-supercapacitors (MSCs) because of their facile ion transport channels. Here, a high-precision controllable photonic-synthesis strategy that provided 1inch wafer-scale ultra-thin film arrays of alloyed WxMo2xSy with sulfur vacancies and expanded interlayer (13.2Å, twice of 2H MoS2) is reported. This strategy regulates the nucleation and growth of transition metal dichalcogenides (TMDs) on the picosecond or even femtosecond scale, which induces Mo-W alloying, interlayer expansion, and sulfur loss. Therefore, the diffusion barrier of WxMo2xSy is reduced, with charge transfer and ion diffusion enhancing. The as-prepared symmetric MSCs with the size of 100×100µm2 achieve ultrahigh specific capacitance (242.57mFcm-2 and 242567.83Fcm-3), and energy density (21.56Whcm-3 with power density of 485.13Wcm3). The established synthesis strategy fits numerous materials, which provides a universal method for the flexible synthesis of electrodes in microenergy devices.

Direct synthesis of controllable ultrathin heteroatoms-intercalated 2D layered materials

Two-dimensional (2D) layered materials have been studied in depth during the past two decades due to their unique structure and properties. Transition metal (TM) intercalation of layered materials have been proven as an effective way to introduce new physical properties, such as tunable 2D magnetism, but the direct growth of atomically thin heteroatoms-intercalated layered materials remains untapped. Herein, we directly synthesize various ultrathin heteroatoms-intercalated 2D layered materials (UHI-2DMs) through flux-assisted growth (FAG) approach. Eight UHI-2DMs (V1/3NbS2, Cr1/3NbS2, Mn1/3NbS2, Fe1/3NbS2, Co1/3NbS2, Co1/3NbSe2, Fe1/3TaS2, Fe1/4TaS2) were successfully synthesized. Their thickness can be reduced to the thinnest limit (bilayer 2D material with monolayer intercalated TM), and magnetic ordering can be induced in the synthesized structures. Interestingly, due to the possible anisotropy-stabilized long-range ferromagnetism in Fe1/3TaS2 with weak interlayer coupling, the layer-independent magnetic ordering temperature of Fe1/3TaS2 was revealed by magneto-transport properties. This work establishes a general method for direct synthesis of heteroatom-intercalated ultrathin 2D materials with tunable chemical and physical properties.

Highly conductive Ti3C2 MXene-supported CoAl-layered double hydroxide nanosheets for ultrasensitive electrochemical detection of organophosphate pesticide fenitrothion.

A novel electrochemical method is presented for ultrasensitive detection of the organophosphate pesticide (OPP) fenitrothion by using Ti3C2 MXene/CoAl-LDH nanocomposite as the electrode modifier. The Ti3C2 MXene/CoAl-LDH nanocomposite is synthesized by growing CoAl-LDH in situ on MXene nanosheets. The combination of two ultrathin 2D materials provides more active sites, larger specific surface area, superior adsorption properties, and better electrical conductivity, which leads to rapid electron-transfer and mass-transfer between the substrate electrode and analytes when it is acted as the electrochemical sensing material. In addition, through the chelation of phosphate groups with the Ti defect sites enriched in MXene, OPP is adsorbed on the electrode. Consequently, the corresponding modified electrode gives rise to a wide linear response range of 0.03 ~ 120μmol/L for the differential pulse voltammetry detection of fenitrothion with a low detection limit of 5.8nmol/L (3σ). The method offers good repeatability, stability, selectivity, and practicability for real samples. This strategy provides a reference platform for the electrochemical monitoring of trace OPPs residue by using MXene/LDH-based nanocomposites.

Enabling Efficient Anchoring‐Conversion Interface by Fabricating Double‐Layer Functionalized Separator for Suppressing Shuttle Effect

Lithium‐sulfur batteries (LiSBs) with high energy density still face challenges on sluggish conversion kinetics, severe shuttle effects of lithium polysulfides (LiPSs), and low blocking feature of ordinary separators to LiPSs. To tackle these, a novel double‐layer strategy to functionalize separators is proposed, which consists of Co with atomically dispersed CoN4 decorated on Ketjen black (Co/CoN4@KB) layer and an ultrathin 2D Ti3C2Tx MXene layer. The theoretical calculations and experimental results jointly demonstrate metallic Co sites provide efficient adsorption and catalytic capability for long‐chain LiPSs, while CoN4 active sites facilitate the absorption of short‐chain LiPSs and promote the conversion to Li2S. The stacking MXene layer serves as a microscopic barrier to further physically block and chemically anchor leaked LiPSs from the pores and gaps of the Co/CoN4@KB layer, thus preserving LiPSs within efficient anchoring‐conversion reaction interfaces to balance the accumulation of “dead S” and Li2S. Consequently, with an ultralight loading of Co/CoN4@KB‐MXene, the LiSBs exhibit amazing electrochemical performance even under high sulfur loading and lean electrolyte, and the outperforming performance for lithium‐selenium batteries (LiSeBs) can also be achieved. This work exploits a universal and effective strategy of a double‐layer functionalized separator to regulate the equilibrium adsorption‐catalytic interface, enabling high‐energy and long‐cycle LiSBs/LiSeBs.

Enabling Efficient Anchoring-Conversion Interface by Fabricating Double-Layer Functionalized Separator for Suppressing Shuttle Effect.

Lithium-sulfur batteries (LiSBs) with high energy density still face challenges on sluggish conversion kinetics, severe shuttle effects of lithium polysulfides (LiPSs), and low blocking feature of ordinary separators to LiPSs. To tackle these, a novel double-layer strategy to functionalize separators is proposed, which consists of Co with atomically dispersed CoN4 decorated on Ketjen black (Co/CoN4@KB) layer and an ultrathin 2D Ti3C2Tx MXene layer. The theoretical calculations and experimental results jointly demonstrate metallic Co sites provide efficient adsorption and catalytic capability for long-chain LiPSs, while CoN4 active sites facilitate the absorption of short-chain LiPSs and promote the conversion to Li2S. The stacking MXene layer serves as a microscopic barrier to further physically block and chemically anchor the leaked LiPSs from the pores and gaps of the Co/CoN4@KB layer, thus preserving LiPSs within efficient anchoring-conversion reaction interfaces to balance the accumulation of "dead S" and Li2S. Consequently, with an ultralight loading of Co/CoN4@KB-MXene, the LiSBs exhibit amazing electrochemical performance even under high sulfur loading and lean electrolyte, and the outperforming performance for lithium-selenium batteries (LiSeBs) can also be achieved. This work exploits a universal and effective strategy of a double-layer functionalized separator to regulate the equilibrium adsorption-catalytic interface, enabling high-energy and long-cycle LiSBs/LiSeBs.

A two-dimensional Aurivillius oxide for enhanced solar energy driven hydrogen evolution and waste water treatment

Bi2WO6 has attracted extensive attention in photocatalysts in recent years as a typical Aurivillius oxide. However, it suffers from severe electron-hole recombination due to the large charge transfer distance from bulk to surface. Unfortunately, strong chemical bonds between the neighboring layers in Aurivillius oxides lead to difficulties in the construction of 2D materials. Here, a facile NaBH4-assisted hydrothermal method is developed to construct 2D Bi2WO6 nanosheets with adjustable thickness from 4.03 to 1.51 nm and O vacancies density (named as BWO-x, x = 15, 30, 45, 60). By balancing the thickness and the O vacancy density in the nanosheets, the charge separation efficiency can be tuned and consequently, the photocatalytic activity can be optimized, leading to over 11 times enhancement in photocatalytic hydrogen evolution. Furthermore, the best performed nanosheets demonstrate universality in dye polluted water treatment. Nearly 100% degradation can be reached after only 5, 50, and 30 min with degradation rate constant of 29.73, 3.21, and 6.62 min−1g−1 for Rhodamine B, methyl orange, and methylene blue, respectively. This work provides a comprehensive approach to produce ultrathin 2D nanosheets of Aurivillius photocatalysts for enhanced charge separation and photocatalytic activity.

Enhanced Electron Delocalization Induced by Ferromagnetic Sulfur doped C3N4 Triggers Selective H2O2 Production.

For the 2D metal-free carbon catalysts, the atomic coplanar architecture enables a large number of pz orbitals to overlap laterally, thus forming π-electron delocalization, and the delocalization degree of the central atom dominates the catalytic activity. Herein, designing sulfur-doped defect-rich graphitic carbon nitride (S-Nv-C3N4) materials as a model, we propose a strategy to promote localized electron polarization by enhancing the ferromagnetism of ultra-thin 2D carbon nitride nanosheets. The introduction of sulfur (S) further promotes localized ferromagnetic coupling, thereby inducing long-range ferromagnetic ordering and accelerating the electron interface transport. Meanwhile, the hybridization of sulfur atoms breaks the symmetry and integrity of the unit structure, promotes electron enrichment and stimulating electron delocalization at the active site. This optimization enhances the *OOH desorption, providing a favorable kinetic pathway for the production of hydrogen peroxide (H2O2). Consequently, S-Nv-C3N4 exhibits high selectivity (>95 %) and achieves a superb H2O2 production rate, approaching 4374.8 ppm during continuous electrolysis over 300 hour. According to theoretical calculation and in situ spectroscopy, the ortho-S configuration can provide ferromagnetic perturbation in carbon active centers, leading to the electron delocalization, which optimizes the OOH* adsorption during the catalytic process.

Polymer-functionalized metal-organic framework nanosheet membranes for efficient CO2 capture

Two-dimensional metal-organic frameworks (2DMOFs) have emerged as highly appealing candidates as advanced separation membrane materials. However, constructing 2DMOF membranes with appropriate channel sizes to separate CO2 from N2 remains a great challenge. Here, we propose an in-situ crystallization approach to synthesize CO2-philic-polymer functionalized Zr-based MOF nanosheets, enabling the fabrication of efficient CO2 capture membranes. The in-situ MOF crystallization with polyethylenimine (PEI) polymers leads to a uniform distribution of amines, resulting in the formation of PEI-NUS hybrid nanosheet characterized by both high porosity and strong affinity to CO2. These nanosheets are assembled into ultrathin lamellar membranes with thicknesses ranging from 40 to 120 nm. The amines of PEI polymers significantly facilitate the CO2 transfer as reaction carriers, resulting in a substantially improved CO2/N2 separation performance with a CO2 permeance of 410 GPU and a CO2/N2 selectivity of 90, which are among the best for MOF membranes in CO2 separation. This in-situ functionalization strategy paves the way for the fabrication of ultrathin 2D membranes for various separations.