Enhanced Performance of Self‐Assembled Monolayer Field‐Effect Transistors with Top‐Contact Geometry through Molecular Tailoring,Heated Assembly,and Thermal Annealing

Low‐voltage self‐assembled monolayer field‐effect transistors (SAMFETs) that operate under an applied bias of less than ?3 V and a high hole mobility of 10^?2 cm² V^?1 s^?1 are reported. A self‐assembled monolayer (SAM) with a quaterthiophene semiconducting core and a phosphonic acid binding group is used to fabricate SAMFETs on both high‐voltage (AlO_x/300 nm SiO₂) and low‐voltage (HfO₂) dielectric platforms. High performance is achieved through enhanced SAM packing density via a heated assembly process and through improved electrical contact between SAM semiconductor and metal electrodes. Enhanced electrical contact is obtained by utilizing a functional methylthio head group combined with thermal annealing post gold source/drain electrode deposition to facilitate the interaction between SAM and electrode.     

2D Heterostructure Membranes with Sunlight‐Driven Self‐Cleaning Ability for Highly Efficient Oil–Water Separation

Introducing solar energy into membrane filtration to decrease energy and chemicals consumption represents a promising direction in membrane fields. In this study, a kind of 0D/2D heterojunction is fabricated by depositing biomineralized titanium dioxide (TiO₂) nanoparticles with delaminated graphitic carbon nitride (g‐C₃N₄) nanosheets, and subsequently a kind of 2D heterostructure membrane is fabricated via intercalating g‐C₃N₄@TiO₂ heterojunctions into adjacent graphene oxide (GO) nanosheets by a vacuum‐assisted self‐assembly process. Due to the enlarged interlayer spacing of GO nanosheets, the initial permeation flux of GO/g‐C₃N₄@TiO₂ membrane reaches to 4536 Lm^?2 h^?1 bar^?1, which is more than 40‐fold of GO membranes (101 Lm^?2 h^?1 bar^?1) when utilized for oil/water separation. To solve the sharp permeation flux decline, arising from the adsorption of oil droplets, the a sunlight‐driven self‐cleaning process is followed, maintaining a flux recovery ratio of more than 95% after ten cycles of filtration experiment. The high permeation flux and excellent sunlight‐driven flux recovery of these heterostructure membranes manifest their attractive potential application in water purification.     

Self‐Assembly of Nanostructured,Complex, Multication Films via Spontaneous Phase Separation and Strain‐Driven Ordering

Spontaneous self‐assembly of a multication nanophase in another multication matrix phase is a promising bottom‐up approach to fabricate novel, nanocomposite structures for a range of applications. In an effort to understand the mechanisms for such self‐assembly, complimentary experimental and theoretical studies are reported to first understand and then control or guide the self‐assembly of insulating BaZrO₃ (BZO) nanodots within REBa₂Cu₃O_7–δ (RE = rare earth elements including Y, REBCO) superconducting films. The strain field developed around BZO nanodots embedded in the REBCO matrix is a key driving force dictating the self‐assembly of BZO nanodots along REBCO c‐axis. The size selection and spatial ordering of BZO self‐assembly are simulated using thermodynamic and kinetic models. The BZO self‐assembly is controllable by tuning the interphase strain field. REBCO superconducting films with BZO defect arrays self‐assembled to align in both vertical (REBCO c‐axis) and horizontal (REBCO ab‐planes) directions result in the maximized pinning and J_c performance for all field angles with smaller angular J_c anisotropy. The work has broad implications for the fabrication of controlled self‐assembled nanostructures for a range of applications via strain‐tuning.     

General Method for Large‐Area Films of Carbon Nanomaterials and Application of a Self‐Assembled Carbon Nanotube Film as a High‐Performance Electrode Material for an All‐Solid‐State Supercapacitor

Rational assembly of carbon nanostructures into large‐area films is a key step to realize their applications in ubiquitous electronics and energy devices. Here, a self‐assembly methodology is devised to organize diverse carbon nanostructures (nanotubes, dots, microspheres, etc.) into homogeneous films with potentially infinite lateral dimensions. On the basis of studies of the redox reactions in the systems and the structures of films, the spontaneous deposition of carbon nanostructures onto the surface of the copper substrate is found to be driven by the electrical double layer between copper and solution. As a notable example, the as‐assembled multiwalled carbon nanotube (MWCNT) films display exceptional properties. They are a promising material for flexible electronics with superior electrical and mechanical compliance characteristics. Finally, two kinds of all‐solid‐state supercapacitors based on the self‐assembled MWCNT films are fabricated. The supercapacitor using carbon cloth as the current collector delivers an energy density of 3.5 Wh kg^?1 and a power density of 28.1 kW kg^?1, which are comparable with the state‐of‐the‐art supercapacitors fabricated by the costly single‐walled carbon nanotubes and arrays. The supercapacitor free of foreign current collector is ultrathin and shows impressive volumetric energy density (0.58 mWh cm^?3) and power density (0.39 W cm^?3) too.     

Programmed High‐Hole‐Mobility Supramolecular Polymers from Disk‐Shaped Molecules

In this paper a simple, casting solution technique for the preparation of two‐dimensional (2D) arrays of very‐high molecular weight (MW) 1D‐Pc supramolecular inorganic polymers is described. The soluble fluoroaluminium tetra‐tert‐butylphthalocyanine (ttbPcAlF) is synthesized and characterized, which can be self‐assembled to form 2D arrays of very‐high‐MW 1D‐Pc supramolecular inorganic polymers. High‐resolution transmission electron microscopy (HRTEM) demonstrates that the 1D‐ttbPcAlF, having a cofacial ring spacing of ～0.36 nm and an interchain distance of ～1.7 nm, self‐assembles into 2D‐nanosheets (～140 nm in length, ～20 nm in width, and equivalent to MW of 3.2 × 10⁵ g mol^?1). The film cast from a 1,2‐dichloroethane (DCE) solution shows a minimum hole‐mobility of ～0.3 cm² V^?1 s^?1 at room temperature by flash‐photolysis time‐resolved microwave conductivity (TRMC) measurements and a fairly high dark dc‐conductivity of ～1 × 10^?3 S cm^?1.     

Self‐Supporting,Double Stimuli‐Responsive Porous Membranes From Polystyrene‐block‐poly(N,N‐dimethylaminoethyl methacrylate) Diblock Copolymers

Asymmetric membranes are prepared via the non‐solvent‐induced phase separation (NIPS) process from a polystyrene‐block‐poly(N,N‐dimethylaminoethyl methacrylate) (PS‐b‐PDMAEMA) block copolymer. The polymer is prepared via sequential living anionic polymerization. Membrane surface and volume structures are characterized by scanning electron microscopy. Due to their asymmetric character, resulting in a thin separation layer with pores below 100 nm on top and a macroporous volume structure, the membranes are self‐supporting. Furthermore, they exhibit a defect‐free surface over several 100 µm². Polystyrene serves as the membrane matrix, whereas the pH‐ and temperature‐sensitive minority block, PDMAEMA, renders the material double stimuli‐responsive. Therefore, in terms of water flux, the membranes are able to react on two independently applicable stimuli, pH and temperature. Compared to the conditions where the lowest water flux is obtained, low temperature and pH, activation of both triggers results in a seven‐fold permeability increase. The pore size distribution and the separation properties of the obtained membranes were tested through the pH‐dependent filtration of silica particles with sizes of 12–100 nm.     

TpyCo2+‐Based Coordination Polymers by Water‐Induced Gelling Trigged Efficient Oxygen Evolution Reaction

Though the use of conventional self‐assembled architectures in functional applications involving advanced energy chemistries is an important research area, it remains largely unexplored. The self‐assembly of the threefold and sixfold‐symmetric terpyridines (tpy) with Co(II) salts results in a novel morphological and structural characteristics, regardless of the nature of the self‐assembled fragments. Herein, such metallopolymers are achieved by one‐pot synthesis in CH₃OH/CHCl₃ (v/v = 5:1) mixture ambient. It is found, for the first time, that Co‐containing polymers can be well dispersed in deionized water to form gel‐like self‐assemblies that consist of a highly interconnected 3D network and exhibit enhanced electrical conductivity and thus are attractive as electrocatalysts. As expected, the optimized Co‐based polymeric structures exhibit a low overpotential of 320 mV at 10 mA cm^?2 and high stability over 2000 cycles toward oxygen evolution reaction (OER), surpassing commercial RuO₂/C, single‐site Co catalysts, polymer, and metal–organic framework‐based OER catalysts reported to date. X‐ray absorption spectroscopy and density functional theory calculations reveal that the tpy‐Co²⁺ (3N‐Co or tpy‐Co²⁺) configurations act as highly active sites. Importantly, this work demonstrates the functional application of the self‐assembled metallopolymers as electrocatalysts for energy conversion.     

Preparation and Memory Performance of a Nanoaggregated Dispersed Red 1‐Functionalized Poly (N‐vinylcarbazole) Film via Solution‐Phase Self‐Assembly

A nanoaggregated dispersed red 1‐grafted poly(N‐vinylcarbazole) (abbreviated PVDR) is self‐assembled via π–π stacking interactions of the carbazole groups in the polymer system after adding a solution of PVDR in N,N‐dimethylformamide to dichloromethane. Upon self‐assembly, the nanoaggregated PVDR film displays helical columnar stacks with large grain sizes, whereas a non‐aggregated PVDR film exhibits an amorphous morphology with smaller grain size. A write‐once read‐many‐times (WORM) memory device is shown whereby a pre‐assembled solution of PVDR is spin‐coated as the active layer and is sandwiched between an aluminum electrode and an indium‐tin‐oxide (ITO) electrode. This device shows very good memory performance, with an ON/OFF current ratio of more than 10⁵ and a low misreading rate through the precise control of the ON and OFF states. The stability of the nanoaggregated PVDR device is much higher than that of the non‐nanoaggregated PVDR device. This difference in device stability under constant voltage stress can be mainly attributed to the difference in the film crystallinity and surface morphology. No degradation in current density was observed for the ON‐ and OFF‐states after more than one hundred million (10⁸) continuous read cycles indicating that both states were insensitive to the read cycles. These results render the nanoaggregated PVDR polymer as promising components for high‐performance polymer memory devices.     

Quantum‐Dot‐Functionalized Poly(styrene‐co‐acrylic acid) Microbeads: Step‐Wise Self‐Assembly,Characterization, and Applications for Sub‐femtomolar Electrochemical Detection of DNA Hybridization

A novel nanoparticle label capable of amplifying the electrochemical signal of DNA hybridization is fabricated by functionalizing poly(styrene‐co‐acrylic acid) microbeads with CdTe quantum dots. CdTe‐tagged polybeads are prepared by a layer‐by‐layer self‐assembly of the CdTe quantum dots (diameter = 3.07 nm) and polyelectrolyte on the polybeads (diameter = 323 nm). The self‐assembly procedure is characterized using scanning and transmission electron microscopy, and X‐ray photoelectron, infrared and photoluminescence spectroscopy. The mean quantum‐dot coverage is (9.54 ± 1.2) × 10³ per polybead. The enormous coverage and the unique properties of the quantum dots make the polybeads an effective candidate as a functionalized amplification platform for labelling of DNA or protein. Herein, as an example, the CdTe‐tagged polybeads are attached to DNA probes specific to breast cancer by streptavidin–biotin binding to construct a DNA biosensor. The detection of the DNA hybridization process is achieved by the square‐wave voltammetry of Cd²⁺ after the dissolution of the CdTe tags with HNO₃. The efficient carrier‐bead amplification platform, coupled with the highly sensitive stripping voltammetric measurement, gives rise to a detection limit of 0.52 fmol L^?1 and a dynamic range spanning 5 orders of magnitude. This proposed nanoparticle label is promising, exhibits an efficient amplification performance, and opens new opportunities for ultrasensitive detection of other biorecognition events.     

Self‐Assembled,Millimeter‐Sized TIPS‐Pentacene Spherulites Grown on Partially Crosslinked Polymer Gate Dielectric

Here, a highly crystalline and self‐assembled 6,13‐bis(triisopropylsilylethynyl) pentacene (TIPS‐Pentacene) thin films formed by simple spin‐coating for the fabrication of high‐performance solution‐processed organic field‐effect transistors (OFETs) are reported. Rather than using semiconducting organic small‐molecule–insulating polymer blends for an active layer of an organic transistor, TIPS‐Pentacene organic semiconductor is separately self‐assembled on partially crosslinked poly‐4‐vinylphenol:poly(melamine‐co‐formaldehyde) (PVP:PMF) gate dielectric, which results in a vertically segregated semiconductor‐dielectric film with millimeter‐sized spherulite‐crystalline morphology of TIPS‐Pentacene. The structural and electrical properties of TIPS‐Pentacene/PVP:PMF films have been studied using a combination of polarized optical microscopy, atomic force microscopy, 2D‐grazing incidence wide‐angle X‐ray scattering, and secondary ion mass spectrometry. It is finally demonstrated a high‐performance OFETs with a maximum hole mobility of 3.40 cm² V^?1 s^?1 which is, to the best of our knowledge, one of the highest mobility values for TIPS‐Pentacene OFETs fabricated using a conventional solution process. It is expected that this new deposition method would be applicable to other small molecular semiconductor–curable polymer gate dielectric systems for high‐performance organic electronic applications.     

Electrochemically Triggered Selective Adsorption of Biotemplated Nanoparticles on Self‐Assembled Organometallic Diblock Copolymer Thin Films

The controlled adsorption of the iron‐containing cage protein ferritin at the nanoscale using stimuli‐responsive self‐assembled diblock copolymer thin‐film templates is reported. The diblock copolymer used study consists of a cylinder‐forming polystyrene‐block‐polyferrocenylsilane (PS‐b‐PFS), with PFS as the minor block, and shows reversible redox properties. To prevent any spontaneous protein adsorption on either block, the electrolyte pH is selected to leave the ferritin negatively charged, and the protein concentration and solution ionic strength are carefully tuned. Selective adsorption of ferritin on the PFS domains of the self‐assembled thin films is then triggered in situ by applying a positive potential, simultaneously oxidizing the PFS and attracting the ferritin electrostatically.     

Surface‐Shielding Nanostructures Derived from Self‐Assembled Block Copolymers Enable Reliable Plasma Doping for Few‐Layer Transition Metal Dichalcogenides

Precise modulation of electrical and optical properties of 2D transition metal dichalcogenides (TMDs) is required for their application to high‐performance devices. Although conventional plasma‐based doping methods have provided excellent controllability and reproducibility for bulk or relatively thick TMDs, the application of plasma doping for ultrathin few‐layer TMDs has been hindered by serious degradation of their properties. Herein, a reliable and universal doping route is reported for few‐layer TMDs by employing surface‐shielding nanostructures during a plasma‐doping process. It is shown that the surface‐protection oxidized polydimethylsiloxane nanostructures obtained from the sub‐20 nm self‐assembly of Si‐containing block copolymers can preserve the integrity of 2D TMDs and maintain high mobility while affording extensive control over the doping level. For example, the self‐assembled nanostructures form periodically arranged plasma‐blocking and plasma‐accepting nanoscale regions for realizing modulated plasma doping on few‐layer MoS₂, controlling the n‐doping level of few‐layer MoS₂ from 1.9 × 10¹¹ cm^?2 to 8.1 × 10¹¹ cm^?2 via the local generation of extra sulfur vacancies without compromising the carrier mobility.     

Anisotropy of Charge Transport in a Uniaxially Aligned and Chain‐Extended,High‐Mobility,Conjugated Polymer Semiconductor

Charge transport in the ribbon phase of poly(2,5‐bis(3‐alkylthiophen‐2‐yl)thieno[3,2‐b]thiophene) (PBTTT)—one of the most highly ordered, chain‐extended crystalline microstructures available in a conjugated polymer semiconductor—is studied. Ribbon‐phase PBTTT has previously been found not to exhibit high carrier mobilities, but it is shown here that field‐effect mobilities depend strongly on the device architecture and active interface. When devices are constructed such that the ribbon‐phase films are in contact with either a polymer gate dielectric or an SiO₂ gate dielectric modified by a hydrophobic, self‐assembled monolayer, high mobilities of up to 0.4 cm² V^?1 s^?1 can be achieved, which is comparable to those observed previously in terrace‐phase PBTTT. In uniaxially aligned, zone‐cast films of ribbon‐phase PBTTT the mobility anisotropy is measured for transport both parallel and perpendicular to the polymer chain direction. The mobility anisotropy is relatively small, with the mobility along the polymer chain direction being higher by a factor of 3–5, consistent with the grain size encountered in the two transport directions.     

Fuel Cell Membrane Electrode Assemblies Fabricated by Layer‐by‐Layer Electrostatic Self‐Assembly Techniques

High activity, carbon supported Pt electrocatalysts were synthesized using a supercritical fluid method and a selective heterogeneous nucleation reaction to disperse Pt onto single walled carbon nanotube and carbon fiber supports. These nanocomposite materials were then incorporated into catalyst and gas diffusion layers consisting of polyelectrolytes, i.e., Nafion, polyaniline, and polyethyleneimine using layer‐by‐layer (LBL) assembly techniques. Due to the ultrathin nature and excellent homogeneity characteristics of LBL materials, the LBL nanocomposite catalyst layers (LNCLs) yielded much higher Pt utilizations, 3,198 mW mg_Pt^?1, than membrane electrode assemblies produced using conventional methods (～800 mW mg_Pt^?1). Thinner membranes (100 bilayers) can further improve the performance of the LNCLs and these layers can function as catalyzed gas diffusion layers for the anode and cathode of a polymer electrolyte membrane fuel cell.     

All‐Carbon Nanoarchitectures as High‐Performance Separation Membranes with Superior Stability

The application of graphene‐based membranes is hindered by their poor stability under practical hydrodynamic conditions. Here, nanocarbon architectures are designed by intercalating surface‐functionalized, small‐diameter, multi‐walled carbon nanotubes (MWCNTs) into reduced graphene oxide (rGO) sheets to create highly stable membranes with improved water permeability and enhanced membrane selectivity. With the intercalation of 10 nm diameter MWCNTs, the water permeability reaches 52.7 L m^?2 h^?1 bar^?1, which is 4.8 times that of pristine rGO membrane and five to ten times higher than most commercial nanofiltration membranes. The membrane also attains almost 100% rejection for three organic dyes of different charges. More importantly, the membrane can endure a turbulent hydrodynamic flow with cross‐flow rates up to 2000 mL min^?1 and a Reynolds number of 4667. Physicochemical characterization reveals that the inner graphitic walls of the MWCNTs can serve as spacers, while nanoscale rGO foliates on the outer walls interconnect with the assimilated rGO sheets to instill superior membrane stability. In contrast, intercalating with single‐walled nanotubes fails to reproduce such stability. Overall, this nanoarchitectured design is highly versatile in creating both graphene‐rich and CNT‐rich all‐carbon membranes with engineered nanochannels, and is regarded as a general approach in obtaining stable membranes for realizing practical applications of graphene‐based membranes.     

Non‐Covalent Functionalization of Graphene Using Self‐Assembly of Alkane‐Amines

A simple, versatile method for non‐covalent functionalization of graphene based on solution‐phase assembly of alkane‐amine layers is presented. Second‐order Møller–Plesset (MP2) perturbation theory on a cluster model (methylamine on pyrene) yields a binding energy of ≈220 meV for the amine–graphene interaction, which is strong enough to enable formation of a stable aminodecane layer at room temperature. Atomistic molecular dynamics simulations on an assembly of 1‐aminodecane molecules indicate that a self‐assembled monolayer can form, with the alkane chains oriented perpendicular to the graphene basal plane. The calculated monolayer height (≈1.7 nm) is in good agreement with atomic force microscopy data acquired for graphene functionalized with 1‐aminodecane, which yield a continuous layer with mean thickness ≈1.7 nm, albeit with some island defects. Raman data also confirm that self‐assembly of alkane‐amines is a non‐covalent process, i.e., it does not perturb the sp² hybridization of the graphene. Passivation and adsorbate n‐doping of graphene field‐effect devices using 1‐aminodecane, as well as high‐density binding of plasmonic metal nanoparticles and seeded atomic layer deposition of inorganic dielectrics using 1,10‐diaminodecane are also reported.     

Tailoring Rod‐Like FeSe2 Coated with Nitrogen‐Doped Carbon for High‐Performance Sodium Storage

Designing potential anodes for sodium‐ion battery with both remarkable durability and high‐rate capability has captured enormous attention so far. The engineering of size and morphology is deemed as an effective manner to boost the electrochemical properties. Owing to the anisotropic self‐assembly of iron selenide, rod‐like FeSe₂ coates with nitrogen‐doped carbon is prepared through the thermal reaction of Prussian blue with selenium. Notably, the cyano groups are effectively transformed into N‐doped carbon with Fe? N? C bonds, which uniformly coats FeSe₂, prompting Na⁺ transportations. Interestingly, the particle size is tailored by heating rates, along with increased carbon content, leading to broadened energy levels for redox reaction. Bestowed by these advantages, the FeSe₂/N‐C as Na‐storage anode delivers impressive electrochemical properties. Even at a rather high rate of 10.0 A g^?1, a considerable capacity of 308 mAh g^?1 is yielded over 10 000 loops. Supported by the detailed analysis of kinetic features, reduced size of particles could bring about the enhanced contributions of pseudocapacitive and quickening rate of ions transferring. The phase evolutions are further investigated by in situ EIS and ex‐situ technologies. The work is expected to provide a new strategy to prepare metal‐selenide with controllable size and induce the faster kinetic of high‐rate materials.     

Tough and Self‐Recoverable Thin Hydrogel Membranes for Biological Applications

Tough and self‐recoverable hydrogel membranes with micrometer‐scale thickness are promising for biomedical applications, which, however, rarely be realized due to the intrinsic brittleness of hydrogels. In this work, for the first time, by combing noncovalent DN strategy and spin‐coating method, we successfully fabricated thin (thickness: 5–100 µm), yet tough (work of extension at fracture: 10⁵–10⁷ J m^?3) and 100% self‐recoverable hydrogel membranes with high water content (62–97 wt%) in large size (≈100 cm²). Amphiphilic triblock copolymers, which form physical gels by self‐assembly, were used for the first network. Linear polymers that physically associate with the hydrophilic midblocks of the first network, were chosen for the second network. The inter‐network associations serve as reversible sacrificial bonds that impart toughness and self‐recovery properties on the hydrogel membranes. The excellent mechanical properties of these obtained tough and thin gel membranes are comparable, or even superior to many biological membranes. The in vitro and in vivo tests show that these hydrogel membranes are biocompatible, and postoperative nonadhesive to neighboring organs. The excellent mechanical and biocompatible properties make these thin hydrogel membranes potentially suitable for use as biological or postoperative antiadhesive membranes.     

Eliminating the Trade‐Off between the Throughput and Pattern Quality of Sub‐15 nm Directed Self‐Assembly via Warm Solvent Annealing

The directed self‐assembly (DSA) of block copolymers (BCPs) has been suggested as a promising nanofabrication solution. However, further improvements of both the pattern quality and manufacturability remain as critical challenges. Although the use of BCPs with a high Flory‐Huggins interaction parameter (χ) has been suggested as a potential solution, this practical self‐assembly route has yet to be developed due to their extremely slow self‐assembly kinetics. In this study, it is reported that warm solvent annealing (WSA) in a controlled environment can markedly improve both the self‐assembly kinetics and pattern quality. A means of avoiding the undesirable trade‐off between the quality and formation throughput of the self‐assembled patterns, which is a dilemma which arises when using the conventional solvent vapor treatment, is suggested. As a demonstration, the formation of well‐defined 13‐nm‐wide self‐assembled patterns (3σ line edge roughness of ≈2.50 nm) in treatment times of 0.5 min (for 360‐nm‐wide templates) is shown. Self‐consistent field theory (SCFT) simulation results are provided to elucidate the mechanism of the pattern quality improvement realized by WSA.     

Submicrometer‐Sized ZIF‐71 Filled Organophilic Membranes for Improved Bioethanol Recovery: Mechanistic Insights by Monte Carlo Simulation and FTIR Spectroscopy

Template‐free self‐assembly synthesis of nano‐sized metal‐organic frameworks (MOFs) is of particular interest in MOF research since organized nanostructures possessing distinctive properties are useful for many advanced applications. In this work, the facile room temperature synthesis of robust submicrometer‐sized ZIF‐71 crystals with different particle sizes (140, 290, or 430 nm), having a high permanent microporosity (S_BET = 827 cm² g^?1) and synthesis yield up to 80% based on Zn on a gram‐scale, is reported. These small ZIF‐71 particles are ideal filler for the fabrication of thinner and homogeneous polydimethylsiloxane (PDMS) based mixed matrix membranes (MMMs) with excellent filler dispersion and filler‐polymer adhesion at high loading up to 40 wt%, as confirmed by scanning electron microscopy. Pervaporation tests using these submicrometer‐sized ZIF‐71 filled MMMs show significant improvement for bioethanol recovery. Interesting phenomena of i) reversible ethanol‐ethanol hydrogen interaction in the ethanol liquid‐phase and ii) irreversible hydrogen interaction of ethanol and –Cl functional group in the α‐cages and octagonal prismatic cages of ZIF‐71 in ethanol vapor‐phase are discovered for the first time by a Fourier transform infrared spectroscopy (FTIR) study. In full agreement with molecular simulation results, these explain fundamentally the ZIF‐71 filled MMMs pervaporation performance.