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Discovering and constructing molecular functionality platforms for materials chemistry innovation has been a persistent target in the fields of chemistry, materials, and engineering. Around this task, basic scientific questions can be asked, novel functional materials can be synthesized, and efficient system functionality can be established. Poly(ionic liquid)s (PILs) have attracted growing interest far beyond polymer science and are now considered an interdisciplinary crossing point between multiple research areas due to their designable chemical structure, intriguing physicochemical properties, and broad and diverse applications. Recently, we discovered that 1,2,4-triazolium-type PILs show enhanced performance profiles, which are due to stronger and more abundant supramolecular interactions ranging from hydrogen bonding to metal coordination, when compared with structurally similar imidazolium counterparts. This phenomenon in our view can be related to the smart hydrogen atoms (SHAs), that is, any proton that binds to the carbon in the N-heterocyclic cations of 1,2,4-triazolium-type PILs. The replacement of one carbon by an electron-withdrawing nitrogen atom in the broadly studied heterocyclic imidazolium ring will further polarize the C–H bond (especially for C5–H) of the resultant 1,2,4-triazolium cation and establish new chemical tools for materials design. For instance, the H-bond-donating strength of the SHA, as well as its Bro̷nsted acidity, is increased. Furthermore, polycarbene complexes can be readily formed even in the presence of weak or medium bases, which is by contrast rather challenging for imidazolium-type PILs. The combination of SHAs with the intrinsic features of heterocyclic cation-functionalized PILs (e.g., N-coordination capability and polymeric multibinding effects) enables new phenomena and therefore innovative materials applications. In this Account, recent progress on SHAs is presented. SHA-related applications in several research branche

The use of block copolymers as a sacrificial template has been demonstrated to be a powerful method for obtaining porous carbons as electrode materials in energy storage devices. In this work, a block copolymer of polystyrene and polyacrylonitrile (PS−b−PAN) has been used as a precursor to produce fibers by electrospinning and powdered carbons, showing high carbon yield (~50%) due to a low sacrificial block content (fPS ≈ 0.16). Both materials have been compared structurally (in addition to comparing their electrochemical behavior). The porous carbon fibers showed superior pore formation capability and exhibited a hierarchical porous structure, with small and large mesopores and a relatively high surface area (~492 m2/g) with a considerable quantity of O/N surface content, which translates into outstanding electrochemical performance with excellent cycle stability (close to 100% capacitance retention after 10,000 cycles) and high capacitance value (254 F/g measured at 1 A/g).

In this communication, a one-step synthetic route is reported toward free-standing metal-nanoparticle-functionalized gradient porous polyelectrolyte membranes (PPMs). The membranes are produced by soaking a glass-plate-supported blend film that consists of a hydrophobic poly(ionic liquid) (PIL), poly(acrylic acid), and a metal salt, into an aqueous hydrazine solution. Upon diffusion of water and hydrazine molecules into the blend film, a phase separation process of the hydrophobic PIL and an ionic crosslinking reaction via interpolyelectrolyte complexation occur side by side to form the PPM. Simultaneously, due to the reductive nature of hydrazine, the metal salt inside the polymer blend film is reduced in situ by hydrazine into metal nanoparticles that anchor onto the PPM. The as-obtained hybrid porous membrane is proven functional in the catalytic reduction of p-nitrophenol. This one-step method to grow metal nanoparticles and gradient porous membranes can simplify future fabrication processes of multifunctional PPMs.

Sand, an abundant resource from the nature, is a promising candidate for oil/water separation. Herein, raw sand was designed with switchable surface wettability to enable recyclability and versatility in practical oil/water separation. The smart sand was fabricated by grafting pH-responsive poly(4-vinylpyridine) (P4VP) and oleophilic/hydrophobic octadecyltrimethoxysilane (OTS) onto its surface. The decorated sand can be used as the oil sorbent for controllable oil sorption and desorption in response to different pHs, as well as a filter to selectively separate either oil or water on demand. This novel design offers an intelligent, low-cost, large-scale, and highly efficient route to potentially settle the issues of industrial oily wastewater and oil spill.

Solar powered clean water production has been considered a favorable way to address the problem of the global water shortage. Recently, the interfacial solar-steam generation system has greatly improved water evaporation by localizing the solar energy at an advanced solar-thermal conversion material interface. However, the specific water productivity (SWP) is still far away from a satisfactory level due to the strong mutual interference between the incident sunlight and the generated water vapor, which causes a huge loss in energy and in turn restrains the final efficiency in water evaporation and collection. SWP is the water collection per solar radiation area per hour, which reflects the actual solar efficiency for water production and a key concern in desalination. Herein, we report a rational Janus-interface solar-steam generator (J-SSG), which separates the water evaporation and the solar-thermal conversion on the two sides of the film generator. This J-SSG demonstrates a water evaporation rate of up to 2.21 kg m(-2) h(-1) under 1 sun in a large area of 100 cm(2). More importantly, a record high SWP of 1.95 kg m(-2) h(-1) is realized in a simple system, and the SWP efficiency corresponding to the ratio of SWP to evaporation rate is as high as 88%. In an outdoor test (Beijing, solar energy similar to 15 MJ m(-2) day(-1)), 10 L purified water per square meter have been easily achieved. This Janus-interface engineering of the solar-steam generator provides a novel strategy and solution for solar powered water production of practical significance.

The structural tailoring of pores is essential to high-performance Fe/N/C electrocatalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. Current strategies for pore structure engineering are usually accompanied with a drastic change of the intrinsic activity-related surface, which may mask the real effects of the porous structure on ORR activity. Herein, a mild carbon dioxide (CO2) etching method was used to flexibly tailor the pore structure of Fe/N/C electrocatalysts without drastic changes in their surface structure and property. In this way, via employing the Fe/N/C electrocatalysts as a model, the intrinsic impact of the pore structure on ORR activity was revealed. In addition, the CO2 etching method developed a high-quality electrocatalyst (sample Fe/N/C–5% CO2) with polarization performance exceeding that of the commercial Pt/C catalyst in the fuel cell working voltage region (>0.65 V). This work will promote the ongoing intensive studies on the rational design of the pore structures in the Fe/N/C electrocatalysts.

The identification of the generation pathway of •OH radical during the oxygen reduction reaction (ORR) is critical because it determines which strategy should be adopted to minimize these corrosive species. In this way, researchers can develop a more stable Fe/N/C ORR catalyst or a catalyst layer in the proton exchange membrane fuel cells (PEMFCs). To date, this critical problem has still been unresolved. Herein, the generation of the •OH radical during the acidic ORR was mimicked by using two known pathways, that is, the Fenton (and Fenton-like) and the electrochemical reduction of H2O2(H2O2-ECR) process. The latter was determined as the main generation pathway of •OH radical below 30 °C. As the temperature surpassed 30 °C, the H2O2-ECR process began to lose its dominance because of the appearance of a third so-far unknown generation pathway. This work lays a basis for future development of radical elimination strategies to stabilize a Fe/N/C ORR catalyst or a catalyst layer in PEMFCs.

Herein, the fabrication of iron-containing porous polyelectrolyte membranes (PPMs) via ionic complexation between an imidazolium-based poly(ionic liquid) (PIL) and 1,1-ferrocenedicarboxylic acid is reported. The key parameters to control the microstructure of porous hybrid membranes are investigated in detail. Further aerobic pyrolysis of such porous hybrid membranes at 900 °C can transfer the ferrocene-containing PPMs into freestanding porous iron oxide films. This process points out a sacrificial template function of porous poly(ionic liquid) membranes in the fabrication of porous metal oxide films.

We report that continuous MOF films with highly controlled thickness (from 44 to 5100 nm) can be deposited over length scales greater than 80 centimeters by a facile, fast, and cost-effective spray-coating method. Such success relies on our discovery of unprecedented perfectly dispersed colloidal solutions consisting of amorphous MOF nanoparticles, which we adopted as precursors that readily converted to the crystalline films upon low-temperature in situ heating. The colloidal solutions allow for the fabrication of compact and uniform MOF films on a great deal of substrates such as fluorine-doped tin oxide, glass, SiO2, Al2O3, Si, Cu, and even flexible polycarbonate, widening their technological applications where substrates are essential. Despite the present work focuses on the fabrication of uniform cobalt-(2-methylimidazole)2 and zinc-(2-methylimidazole)2 films, our findings mark a great possibility in producing other high-quality MOF thin films on a large scale.

This study deals with the facile synthesis of Fe1−xS nanoparticle-containing nitrogen-doped porous carbon membranes (denoted as Fe1−xS/N-PCMs) via vacuum carbonization of hybrid porous poly(ionic liquid) (PIL) membranes, and their successful use as a sulfur host material to mitigate the shuttle effect in lithium–sulfur (Li–S) batteries. The hybrid porous PIL membranes as the sacrificial template were prepared via ionic crosslinking of a cationic PIL with base-neutralized 1,1′-ferrocenedicarboxylic acid, so that the iron source was molecularly incorporated into the template. The carbonization process was investigated in detail at different temperatures, and the chemical and porous structures of the carbon products were comprehensively analyzed. The Fe1−xS/N-PCMs prepared at 900 °C have a multimodal pore size distribution with a satisfactorily high surface area and well-dispersed iron sulfide nanoparticles to physically and chemically confine the LiPSs. The sulfur/Fe1−xS/N-PCM composites were then tested as electrodes in Li–S batteries, showing much improved capacity, rate performance and cycle stability, in comparison to iron sulfide-free, nitrogen-doped porous carbon membranes.

Graphene oxide (GO) is a classic two dimensional (2D) building block that can be used to develop high-performance materials for numerous applications, particularly in the energy and environmental fields. Currently, the precise assembly of GO nanosheets into macroscopic nanohybrids of superior strength and toughness is desirable, and faces challenges and trade-offs. Herein, we exploited the freshly established polycationitrile method as a powerful molecular crosslinking strategy to engineer ultratough and ultrastrong GO/polymer hybrid films, in which a covalent triazine-based network was constructed in a mild condition to reinforce the interface between GO nanosheets. The tensile strength and toughness reached 585 +/- 25 MPa and 14.93 +/- 1.09 MJ m(-3), respectively, which, to the best of our knowledge, are the current world records in all GO-based hybrid films. As an added merit of the tailor-made polymer crosslinker, the high mechanical performance can be maintained in large part at an extremely high relative humidity of 98%. This emerging interface-engineering approach paves a new avenue to produce integrated strong-and-tough 2D nanohybrid materials that are useful in aerospace, artificial muscle, energy harvesting, tissue engineering and more.

A series of organic phosphonic acids (OPAs) were applied as multifunctional spacers to enlarge the inner space of carbide MXene (Ti3C2Tx) laminates. A synergistic improvement in permeance, rejection and stability is achieved via introducing OPA to create pillared laminates. This strategy provides a universal way to regulate transport channels of MXene-based membranes.

Assembling two-dimensional (2D) materials by polyelectrolyte often suffers from inhomogeneous microstructures due to the conventional mixing-and-simultaneous-complexation procedure (mix-and-complex) in aqueous solution. Herein a mix-then-on-demand-complex concept via on-demand in situ cascade anionization and ionic complexation of 2D materials is raised that drastically improves structural order in 2D assemblies, as exemplified by classical graphene oxide (GO)-based ultrathin membranes. Specifically, in dimethyl sulfoxide, the carboxylic acid-functionalized GO sheets (COOH-GOs) were mixed evenly with a cationic poly(ionic liquid) (PIL) and upon filtration formed a well-ordered layered composite membrane with homogeneous distribution of PIL chains in it; next, whenever needed, it was alkali-treated to convert COOH-GO in situ into its anionized state COO--GO that immediately complexed ionically with the surrounding cationic PIL chains. This mix-then-on-demand-complex concept separates the ionic complexation of GO and polyelectrolytes from their mixing step. By synergistically combining the PIL-induced hydrophobic confinement effect and supramolecular interactions, the as-fabricated nanofiltration membranes carry interface transport nanochannels between GO and PIL, reaching a high water permeability of 96.38 L m(-2) h(-1) bar(-1) at a maintained excellent dye rejection 99.79% for 150 h, exceeding the state-of-the-art GO-based hybrid membranes. The molecular dynamics simulations support the experimental data, confirming the interface spacing between GO and PIL as the water transport channels.

Both imidazolium and 1,2,4-triazolium cations are important functional moieties widely incorporated as building blocks in poly(ionic liquid)s (PILs). In a classical model, a PIL usually contains either imidazolium or 1,2,4-triazolium in its repeating unit. Herein, via exploiting the slight reactivity difference of alkyl bromide with imidazole and 1,2,4-triazole at room temperature, we synthesized dual-cationic PIL homopolymers carrying both imidazolium and 1,2,4-triazolium moieties in the same repeating unit, that is, an asymmetrically dicationic unit. We investigated their fundamental properties, for example, thermal stability and solubility, as well as their unique function in forming supramolecular porous membranes via a water-initiated phase-separation and cross-linking process. With such knowledge, we identified a water-based fabricate strategy toward air-stable porous membranes from single-component Pits. This study will enrich the design tools and chemical structure library of PILs and expand their application spectrum.

An Fe/N/C catalyst derived from the pyrolysis of metal-organic frameworks, for example, a zeolitic-imidazolate-framework-8 (ZIF-8), has been regarded as one of the most promising non-precious metal catalysts toward oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). However, its ORR mass activity is still much inferior to that of Pt, partly because of the lack of general and efficient synthetic strategies. Herein, a general carboxylate-assisted strategy that dramatically enhances the ORR mass activity of ZIF-derived Fe/N/C catalysts is reported. The carboxylate is found to promote the formation of Fe/N/C catalysts with denser accessible active sites and entangled carbon nanotubes, as well as a higher mesoporosity. These structural advantages make the carboxylate-assisted Fe/N/C catalysts show a 2-10 fold higher ORR mass activity than the common carboxylate-free one in various cases. When applied in H-2-O-2 PEMFCs, the active acetate-assisted Fe/N/C catalyst generates a peak power density of 1.33 W cm(-2), a new record of peak power density for a H-2-O-2 PEMFC with non-Pt ORR catalysts.