Tunable 2D Conjugated Porous Organic Polymer Films for Precise Molecular Nanofiltration and Optoelectronics.

Structural design of 2D conjugated porous organic polymer films (2D CPOPs), by tuning linkage chemistries and pore sizes, provides great adaptability for various applications, including membrane separation. Here, four free-standing 2D CPOP films of imine- or hydrazone-linked polymers (ILP/HLP) in combination with benzene (B-ILP/HLP) and triphenylbenzene (TPB-ILP/HLP) aromatic cores are synthesized. The anisotropic disordered films, composed of polymeric layered structures, can be exfoliated into ultrathin 2D-nanosheets with layer-dependent electrical properties. The bulk CPOP films exhibit structure-dependent optical properties, triboelectric nanogenerator output, and robust mechanical properties, rivaling previously reported 2D polymers and porous materials. The exfoliation energies of the 2D CPOPs and their mechanical behavior at the molecular level are investigated using density function theory (DFT) and molecular dynamics (MD) simulations, respectively. Exploiting the structural tunability, the comparative organic solvent nanofiltration (OSN) performance of six membranes having different pore sizes and linkages to yield valuable trends in molecular weight selectivity is investigated. Interestingly, the OSN performances follow the predicted transport modeling values based on theoretical pore size calculations, signifying the existence of permanent porosity in these materials. The membranes exhibit excellent stability in organic solvents at high pressures devoid of any structural deformations, revealing their potential in practical OSN applications.

A Researcher's Perspective on Unconventional Lab-to-Fab for 2D Semiconductor Devices.

Current silicon technology is on the verge of reaching its performance limits. This aspect, coupled with the global chip shortage, makes a solid case for steering our attention toward the accelerated commercialization of other electronic materials. Among the available suite of emerging electronic materials, two-dimensional materials, including transition metal dichalcogenides (TMDs), exhibit improved short-channel effects, high electron mobility, and integration into CMOS-compatible processing. While these materials may not be able to replace silicon at the current stages of development, they can supplement Si in the form of Si-compatible CMOS processing and be manufactured for tailored applications. However, the major hurdle in the path of commercialization of such materials is the difficulty in producing their wafer-scale forms, which are not necessarily single crystalline but on a large scale. Recent but exploratory interest in 2D materials from industries, such as TSMC, necessitates an in-depth analysis of their commercialization potential based on trends and progress in entrenched electronic materials (Si) and ones with a short-term commercialization potential (GaN, GaAs). We also explore the possibility of unconventional fabrication techniques, such as printing, for 2D materials becoming more mainstream and being adopted by industries in the future. In this Perspective, we discuss aspects to optimize cost, time, thermal budget, and a general pathway for 2D materials to achieve similar milestones, with an emphasis on TMDs. Beyond synthesis, we propose a lab-to-fab workflow based on recent advances that can operate on a low budget with a mainstream full-scale Si fabrication unit.

NixCo1-x@NixCo1-xO/NCNT as Trifunctional ORR, OER, and HER Electrocatalysts and its Application in a Zn-Air Battery.

The efficient electrochemical conversion and storage devices can be boosted by the development of cost-effective and durable electrocatalysts. However, simultaneous in-depth understanding of the reaction mechanism is also required. Herein, we report the preparation, characterization, and electrochemical activities of bimetallic NixCo1-x NPs and core-shell NixCo1-x@NixCo1-xO NPs stabilized on N-doped carbon nanotubes (NCNTs). The electrocatalyst is derived from a bimetallic MOF {[Ni0.5Co0.5(bpe)2(N(CN)2)](N(CN)2)·(5H2O)}n (1) via pyrolysis followed by calcination. Pyrolysis of the bimetallic MOF gives rise to bimetallic nanoparticles stabilized on NCNTs, which, when subsequently calcined, leads to the formation of a core-shell structure with a semiconducting oxide shell (NixCo1-xO) encapsulating the NixCo1-x bimetallic NP core. Detailed evaluation of the electrocatalytic performance of NixCo1-x@NixCo1-xO/NCNT proves its worth as a bifunctional catalyst with 380 mV overpotential for oxygen evolution reaction at 10 mA cm-2 current density and 0.87 V (vs RHE) onset for oxygen reduction reaction in the alkaline medium. Additionally, the prepared electrocatalyst efficiently catalyzes the hydrogen evolution reaction with a nominal overpotential of 74 mV (vs RHE) for reaching 10 mA cm-2 current density in acidic medium. The practical applicability of this catalyst is further upheld in the fabrication of a zinc-air battery having high specific capacity with high round-trip efficiency and adequate cycle life. DFT calculations establish that the structure of NixCo1-x@NixCo1-xO/NCNT is crucial for its electrochemical activity since it has the threefold advantages of cooperative charge transfer from Co to Ni, synergistic relationship between the conductive alloy core and semiconducting oxide shell, and a highly conductive N-doped CNT matrix.

Structure, Properties and Applications of Two-Dimensional Hexagonal Boron Nitride.

Hexagonal boron nitride (h-BN) has emerged as a strong candidate for two-dimensional (2D) material owing to its exciting optoelectrical properties combined with mechanical robustness, thermal stability, and chemical inertness. Super-thin h-BN layers have gained significant attention from the scientific community for many applications, including nanoelectronics, photonics, biomedical, anti-corrosion, and catalysis, among others. This review provides a systematic elaboration of the structural, electrical, mechanical, optical, and thermal properties of h-BN followed by a comprehensive account of state-of-the-art synthesis strategies for 2D h-BN, including chemical exfoliation, chemical, and physical vapor deposition, and other methods that have been successfully developed in recent years. It further elaborates a wide variety of processing routes developed for doping, substitution, functionalization, and combination with other materials to form heterostructures. Based on the extraordinary properties and thermal-mechanical-chemical stability of 2D h-BN, various potential applications of these structures are described.

Modulating Hierarchical Micro/Mesoporosity by a Mixed Solvent Approach in Al-MOF: Stabilization of MAPbBr3 Quantum Dots.

Various hierarchical micro/mesoporous MOFs based on {[Al(µ-OH)(1,4-NDC)]⋅H2 O} (MOF1) with tunable porosities (pore volume and surface area) have been synthesized by assembling AlIII and 1,4-NDC (1,4-naphthalenedicarboxylate) under microwave irradiation by varying water/ethanol solvent ratio. Water/ethanol mixture has played a crucial role in the mesopore generation in MOF1M25 , MOF1M50 , and MOF1M75 , which is achieved by in situ formation of water/ethanol clusters. By adjusting the ratio of water/ethanol, the particle size, surface area and micro/mesopore volume fraction of the MOFs are controlled. Furthermore, reaction time plays a critical role in mesopore formation as realized by varying reaction time for the MOF with 50 % ethanol (MOF1M50 ). Additionally, hierarchical MOF (MOF1M50 ) has been used as a template for the stabilization of MAPbBr3 (MA=methylammonium) perovskite quantum dots (PQDs). MAPbBr3 PQDs are grown inside MOF1M50 , where mesopores control the size of PQDs which leads to quantum confinement.

Stabilization of MAPbBr3 Perovskite Quantum Dots on Perovskite MOFs by a One-Step Mechanochemical Synthesis.

We report a one-step, solvent-free, green approach for the mechanochemical stabilization of hybrid organic-inorganic lead halide (MAPbBr3) perovskite quantum dots (PQDs) within perovskite metal-organic frameworks (MOFs) [MA-M(HCOO)3] [M = Mn and Co; MA = methylammonium (CH3NH3+)]. The perovskite MOF acts as a template and source of MA cations for growing and stabilizing hybrid PQDs. The synthesis of the composite has been carried out mechanochemically, without the use of any external reagents by simply grinding the perovskite MOF with PbBr2. MAPbBr3@MA-Mn(HCOO)3 composite shows high chemical stability in several solvents. Its excellent processability has been demonstrated by using it as an electrode material which shows photoelectrochemical activity in the presence of light.

Photoswitchable J-Aggregated Processable Organogel by Integrating a Photochromic Acceptor.

A novel π-chromophoric 1,4-bis(anthracenylethynyl)benzene (BAB)-based highly emissive J-aggregated organogel has been synthesized and characterized. Single-crystal structure determination of asymmetric π-chromophoric bola-amphiphilic BAB1 (dodecyl and triethyleneglycolmonomethylether containing side chains of bis(anthracenylethynyl)benzene) supports J-aggregation. Further, a photochromic acceptor chromophore, 4,4'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-2-carbaldehyde), is noncovalently encapsulated in the gel and photoswitching studies have been performed based on photochromic Förster resonance energy transfer. The modulated emission of the processable soft material is further exploited for rewritable display. However, BAB2 (dodecyl side chain on both sides) does not show gelation property due to its low solubility.

Dynamic Resolution of Piezosensitivity in Single Crystals of π-Conjugated Molecules.

Targeted synthesis of piezoresponsive small molecules and in-depth understanding of their mechanism is of utmost importance for the development of smart devices. This work reports the synthesis, structure and piezosensitivity of a bola-amphiphile 1,4-bis(pentyloxy)-2,5-bis(2-pyridineethynyl)-benzene (C5-PPB). Depending on the rate of compression, two different phases in C5-PPB can be generated. The ambient-pressure α-phase is stable up to 0.8 GPa, beyond which it undergoes an isostructural transformation to ß-phase, accompanied by a clearly visible elongation of the crystal. This α-to-ß phase transition requires the sample to be compressed slowly. When quickly compressed, phase α persists to about 1.5 GPa, beyond which its amorphization starts, accompanied by the appearance of irregular grooves on the largest faces. Mechanical pressure also affects the optical property of C5-PPB, which shows reversible mechanochromism with a green to cyan transformation in the emission, associated with a 15 nm shift in the maxima. The conductivity of C5-PPB as a direct outcome of its crystal packing has also been studied.

In situ Stabilization of Au and Co Nanoparticles in a Redox-Active Conjugated Microporous Polymer Matrix: Facile Heterogeneous Catalysis and Electrocatalytic Oxygen Reduction Reaction Activity.

We report a novel in situ method for synthesis of metal nanoparticles (NPs)-CMP (conjugated microporous polymer) composites based on a redox-active, donor-acceptor CMP, tris-(4-aminophenyl)amine (TPA)-perylenediimide (PDI). The TPA-PDI CMP, comprising triphenylamine as an electron donor and PDI as an acceptor, showed stable charge-separated state and semiconducting behavior. Further, TPA-PDI CMP has been exploited for in situ stabilization of metal (Au and Co) NPs, and two novel nanocomposites (Au@TPA-PDI and Co@TPA-PDI) were prepared. The catalytic reduction of nitro aryls to amino aryls was studied using Au@TPA-PDI, which showed excellent yields and fast kinetics. The CMP itself was found to show good activity as a metal-free oxygen reduction reaction (ORR) electrocatalyst with an onset potential of 0.82 V. Stabilizing merely 2.56 wt % Co nanoparticles in the CMP matrix improved the electrochemical ORR activity of as-synthesized TPA-PDI immensely and showed an onset potential of 0.91 V, which has also been supported by density functional theory (DFT) calculations.

Tetracarboxylate Linker-Based Flexible CuII Frameworks: Efficient Separation of CO2 from CO2/N2 and C2H2 from C2H2/C2H4 Mixtures.

We report the synthesis, structure, and adsorption properties of two new metal-organic frameworks (MOFs) {[Cu2(bpp)3(L1)]·(bpp)·(4H2O)} (1) and {[Cu2(bipy)2(L2)(H2O)2]·(bipy)·(5H2O)} (2) obtained from two different flexible tetracarboxylate linkers (L1 and L2) of variable lengths and flexibility. While 1 comprising CuII, L1, and 1,3-bis(4-pyridyl) propane (bpp) is a 2D MOF with a cage-type structure, 2 consisting of CuII, L2, and 4,4'-bipyridine (bipy) has a 3D twofold interpenetrated structure. Both frameworks manifest permanent porosity, as realized from CO2 adsorption at 195 K. 2 shows excellent CO2/N2 and C2H2/C2H4 adsorption selectivity at 298 K. This has been established by using 2 as a separating medium in a breakthrough column for separating mixtures of CO2/N2 (15:85, v/v) and C2H2/C2H4 (1:99, v/v). The selectivity of 2 toward CO2 over N2 and C2H2 over C2H4 is governed by favorable thermodynamic interactions owing to its structural flexibility, unsaturated metal sites, and polar carboxylate groups. Thus, 2 proves to be an extremely efficient material for specific gas separation.

MOF derived carbon based nanocomposite materials as efficient electrocatalysts for oxygen reduction and oxygen and hydrogen evolution reactions.

The escalating global energy demands and the formidable risks posed by fossil fuels coupled with their rapid depletion have inspired researchers to embark on a quest for sustainable clean energy. Electrochemistry based technologies, e.g., fuel cells, Zn-air batteries or water splitting, are some of the frontrunners of this green energy revolution. The primary concern of such sustainable energy technologies is the efficient conversion and storage of clean energy. Most of these technologies are based on half-cell reactions like oxygen reduction, oxygen and hydrogen evolution reactions, which in turn depend on noble metal based catalysts for their efficient functioning. In order to make such green energy technologies economically viable, the need of the hour is to develop new noble metal free catalysts. Porous carbon, with some assistance from heteroatoms like N or S or earth abundant transition metal or metal oxide nanoparticles, has shown excellent potential in the catalysis of such electrochemical reactions. Metal-organic frameworks (MOFs) containing metal nodes and organic linkers in an ordered morphology with inherent porosity are ideal self-sacrificial templates for such carbon materials. There has been a recent spurt in reports on such MOF-derived carbon based materials as electrocatalysts. In this review, we have presented some of this research work and also discussed the practical reasons behind choosing MOFs for this purpose. Different approaches for synthesizing such carbonaceous materials with unique morphologies and doping, targeted towards superior electrochemical activity, have been documented in this review.

Post-synthetic metalation in an anionic MOF for efficient catalytic activity and removal of heavy metal ions from aqueous solution.

A new 3D porous anionic MOF (AMOF-1) based on Zn(II) and a flexible tetracarboxylate linker has been synthesized. AMOF-1 showed potential for capture and removal of toxic metal ions from aqueous solution with a detection limit in the ppm level. The Cu(II)@AMOF-1' hybrid obtained by post-synthetic metalation is studied as a heterogeneous catalyst for the synthesis of benzimidazole derivatives.

A bimodal anionic MOF: turn-off sensing of Cu(II) and specific sensitization of Eu(III.).

A novel porous anionic MOF {[Mg3(ndc)2.5(HCO2)2(H2O)][NH2Me2]·2H2O·DMF} (1) having exchangeable dimethyl amine cations in 1D channels has been synthesized and characterized. Through cation exchange, 1 manifests bimodal functionality, being a turn-off sensor of Cu(II) on one hand, and a selective sensitizer of Eu(III) emitting intense pure red emission on the other.