Soft Template-Based Synthesis of Mesoporous Phosphorus- and Boron-Codoped NiFe-Based Alloys for Efficient Oxygen Evolution Reaction.

Controlling the morphology, composition, and crystalline phase of mesoporous nonnoble metal catalysts is essential for improving their performance. Herein, well-defined P- and B-codoped NiFe alloy mesoporous nanospheres (NiFeB-P MNs) with an adjustable Ni/Fe ratio and large mesopores (11 nm) are synthesized via soft-template-based chemical reduction and a subsequent phosphine-vapor-based phosphidation process. Earth-abundant NiFe-based materials are considered promising electrocatalysts for the oxygen evolution reaction (OER) because of their low cost and high intrinsic catalytic activity. The resulting NiFeB-P MNs exhibit a low OER overpotential of 252 mV at 10 mA cm-2 , which is significantly smaller than that of B-doped NiFe MNs (274 mV) and commercial RuO2 (269 mV) in alkaline electrolytes. Thus, this work highlights the practicality of designing mesoporous nonnoble metal structures and the importance of incorporating P in metallic-B-based alloys to modify their electronic structure for enhancing their intrinsic activity.

Heterostructuring Mesoporous 2D Iridium Nanosheets with Amorphous Nickel Boron Oxide Layers to Improve Electrolytic Water Splitting.

2D heterostructures exhibit a considerable potential in electrolytic water splitting due to their high specific surface areas, tunable electronic properties, and diverse hybrid compositions. However, the fabrication of well-defined 2D mesoporous amorphous-crystalline heterostructures with highly active heterointerfaces remains challenging. Herein, an efficient 2D heterostructure consisting of amorphous nickel boron oxide (Ni-Bi ) and crystalline mesoporous iridium (meso-Ir) is designed for water splitting, referred to as Ni-Bi /meso-Ir. Benefiting from well-defined 2D heterostructures and strong interfacial coupling, the resulting mesoporous dual-phase Ni-Bi /meso-Ir possesses abundant catalytically active heterointerfaces and boosts the exposure of active sites, compared to their crystalline and amorphous mono-counterparts. The electronic state of the iridium sites is tuned favorably by hybridizing with Ni-Bi layers. Consequently, the Ni-Bi /meso-Ir heterostructures show superior and stable electrochemical performance toward both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in an alkaline electrolyte.

Free-standing membranes from the chemical exfoliation of mesoporous amorphous titania thin film.

Thin films are typically bound to their substrate, limiting their integration on rough, porous, curved or chemically/thermally sensitive surfaces. Instead of employing tedious and expensive back-etching processes, specific chemical routes can enable the exfoliation of such thin structures. Herein, we demonstrate that an alkaline treatment can exfoliate a hybrid thin film comprising amorphous titania embedded in well-ordered block-copolymer micelles, which can be redeposited elsewhere. We provide sufficient evidence of the preservation of pore ordering and the importance of neutralizing the solution to spare the system from the redissolution of the titania species.

Direct Z-scheme CuInS2/Bi2MoO6 heterostructure for enhanced photocatalytic degradation of tetracycline under visible light.

The construction of direct Z-scheme heterojunctions with high photocatalytic degradation ability is a theme of importance in both environmental and materials sciences, but still retains many unresolved challenges. In this article, we report the construction of Z-scheme CuInS2/Bi2MoO6 heterostructure by in-situ hydrothermal reactions, demonstrating superior photocatalytic activity towards the degradation of tetracycline under visible light, compared to their individual components: that is to say 8 and 2.5 times those of CuInS2 and Bi2MoO6, respectively. The photocatalytic performance of CuInS2/Bi2MoO6 heterostructure is mainly ascribed to the effective charge transfer at the interface through the construction of a direct Z-scheme heterojunction, combined with a ternary sulfide semiconductor absorbing light in the useful region of the solar spectrum. This photocatalyst provides new insights on the fundamental aspects governing the mechanisms responsible for multicomponent photodegradation, while constituting already a promising candidate for practical environmental applications.

Universal Electrochemical Synthesis of Mesoporous Chalcogenide Semiconductors: Mesoporous CdSe and CdTe Thin Films for Optoelectronic Applications.

Here we report the soft-template-assisted electrochemical deposition of mesoporous semiconductors (CdSe and CdTe). The resulting mesoporous films are stoichiometrically equivalent and contain mesopores homogeneously distributed over the entire surface. To demonstrate the versatility of the method, two block copolymers with different molecular weights are used, yielding films with pores of either 9 or 18 nm diameter. As a proof of concept, the mesoporous CdSe film-based photodetectors show a high sensitivity of 204 mW-1 cm2 at 680 nm wavelength, which is at least two orders of magnitude more sensitive than the bulk counterpart. This work presents a new synthesis route for nanostructured semiconductors with optical band gaps active in the visible spectrum.

Nanostructured mesoporous gold biosensor for microRNA detection at attomolar level.

Advances in nanoarchitectonics enable a wide variety of nanostructured electrodes with tunable shapes and surface for constructing sensitive biosensors. Herein we demonstrate the fabrication of a mesoporous gold (Au) biosensor for the specific and sensitive detection of miRNA in a relatively simple and portable manner. The electrocatalytic activity of the mesoporous Au electrode (MPGE) towards the redox reaction of Fe(CN)6]3-/4- expansively examined. Leveraging the electrocatalytic activity and signal enhancement capacity of the MPGE, an ultrasensitive and specific electrochemical sensor was developed for the detection of microRNA (miRNA). The target miRNA from spiked samples is selectively isolated and purified using magnetic bead-capture probe followed by the direct adsorption on the MPGE through direct affinity interaction between miRNA and mesoporous Au surface. The MPGE-bound miRNA is then quantified by differential pulse voltammetry (DPV) using [Fe(CN)6]4-/3- redox system (Faradaic current decrease with reference to the bare MPGE). This method evades the cumbersome PCR (polymerase chain reaction) and enzymatic amplification steps. This is a single-step assay building which can detect a wide dynamic linear range (100 aM to 1 nM) of miRNA with an ultra-low limit detection of 100 aM and present high translational potentiality for the development of high-performance detection tools for clinics.

Coalescence-Driven Verticality in Mesoporous TiO2 Thin Films with Long-Range Ordering.

Mesoporous semiconducting films with continuous interconnectivity and minimal tortuosity, such as densely ordered arrays of vertical channels, are ideal for ensuring a maximal surface area at the heterojunction to increase the density of charges or photons. While the design of these films with nanostructures below 50 nm using modern lithography is not feasible, continuously perpendicular pores can be obtained throughout a TiO2 film using a traditional soft-templating approach and lyotropic crystal engineering. We demonstrate here that a polystyrene-b-poly(ethylene oxide) block copolymer in a three-solvent system can self-assemble into a body-centered cubic Im3̅m template. The long-range three-dimensional periodicity of the template combined with a high degree of vertical contraction results in coalescence of the pores into orthogonal channels that are strongly interconnected with their nearest neighbors in the (011̅) plane. This work presents evidence of lateral long-range ordering with continuously transverse vertical porosity in a TiO2 material, which will enable functional applications, such as filtration, sensing, catalysis, and optoelectronics. To this end, we demonstrate the ability of the films to template and host methylammonium lead iodide perovskite nanocrystals.

Photodegradation Activity of Poly(ethylene oxide-b-ε-caprolactone)-Templated Mesoporous TiO2 Coated with Au and Pt.

Mesoporous TiO2 films are synthesized through evaporation-induced self-assembly using poly(ethylene oxide-b-ε-caprolactone) diblock copolymers as a soft-template. Using small-angle X-ray scattering and scanning electron microscopy, we investigate the effect of the TiO2/PEO-b-PCL ratio on the resulting nanoarchitectonic structure. After sputter-coating Au and Pt layers, these Au/TiO2 and Pt/TiO2 nanocomposite films display drastically enhanced photodegradation of rhodamine 6G under ultraviolet irradiation, due to the metal films inhibiting the rapid recombination of photogenerated charge carriers.

Designed Patterning of Mesoporous Metal Films Based on Electrochemical Micelle Assembly Combined with Lithographical Techniques.

Mesoporous noble metals and their patterning techniques for obtaining unique patterned structures are highly attractive for electrocatalysis, photocatalysis, and optoelectronics device applications owing to their expedient properties such as high level of exposed active locations, cascade electrocatalytic sites, and large surface area. However, patterning techniques for mesoporous substrates are still limited to metal oxide and silica films, although there is growing demand for developing techniques related to patterning mesoporous metals. In this study, the first demonstration of mesoporous metal films on patterned gold (Au) substrates, prefabricated using photolithographic techniques, is reported. First, different growth rates of mesoporous Au metal films on patterned Au substrates are demonstrated by varying deposition times and voltages. In addition, mesoporous Au films are also fabricated on various patterns of Au substrates including stripe and mesh lines. An alternative fabrication method using a photoresist insulating mask also yields growth of mesoporous Au within the patterning. Moreover, patterned mesoporous films of palladium (Pd) and palladium-copper alloy (PdCu) are demonstrated on the same types of substrates to show versatility of this method. Patterned mesoporous Au films (PMGFs) show higher electrochemically active surface area (ECSA) and higher sensitivity toward glucose oxidation than nonpatterned mesoporous Au films (NMGF).

Solid/Solid Interfacial Architecturing of Solid Polymer Electrolyte-Based All-Solid-State Lithium-Sulfur Batteries by Atomic Layer Deposition.

Solid polymer electrolytes (SPEs)-based all-solid-state lithium-sulfur batteries (ASSLSBs) have attracted extensive research attention due to their high energy density and safe operation, which provide potential solutions to the increasing need for harnessing higher energy densities. There is little progress made, however, in the development of ASSLSBs to improve simultaneously energy density and long-term cycling life, mostly due to the "shuttle effect" of lithium polysulfide intermediates in the SPEs and the low interfacial compatibility between the metal lithium anode and the SPE. In this work, the issues of solid/solid interfacial architecturing through atomic layer deposition of Al2 O3 on poly(ethylene oxide)-lithium bis(trifluoromethanesulfonyl)imide SPE surface are effectively addressed. The Al2 O3 coating promotes the suppression of lithium dendrite formation for over 500 h. ASSLSBs fabricated with two layers of Al2 O3 -coated SPE deliver high gravimetric/areal capacity and Coulombic efficiency, as well as excellent cycling stability and extremely low self-discharge rate. This work provides not only a simple and effective approach to boost the electrochemical performances of SPE-based ASSLSBs, but also enriches the fundamental understanding regarding the underlying mechanism responsible for their performance.

Everlasting Living and Breathing Gyroid 3D Network in Si@SiOx/C Nanoarchitecture for Lithium Ion Battery.

Silicon-based materials are the most promising candidates to surpass the capacity limitation of conventional graphite anode for lithium ion batteries. Unfortunately, Si-based materials suffer from poor cycling performance and dimensional instability induced by the large volume changes during cycling. To resolve such problems, nanostructured silicon-based materials with delicately controlled microstructure and interfaces have been intensively investigated. Nevertheless, they still face problems related to their high synthetic cost and their limited electrochemical properties and thermal stability. To overcome these drawbacks, we demonstrate the strategic design and synthesis of a gyroid three-dimensional network in a Si@SiOx/C nanoarchitecture (3D-Si@SiOx/C) with synergetic interaction between the computational prediction and the synthetic optimization. This 3D-Si@SiOx/C exhibits not only excellent electrochemical performance due to its structural stability and superior ion/electron transport but also enhanced thermal stability due to the presence of carbon, which was formed by a cost-effective one-pot synthetic route. We believe that our rationally designed 3D-Si@SiOx/C will lead to the development of anode materials for the next-generation lithium ion batteries.

Synthesis of Mesoporous TiO2-B Nanobelts with Highly Crystalized Walls toward Efficient H2 Evolution.

Mesoporous TiO2 is attracting increasing interest due to properties suiting a broad range of photocatalytic applications. Here we report the facile synthesis of mesoporous crystalline TiO2-B nanobelts possessing a surface area as high as 80.9 m2 g-1 and uniformly-sized pores of 6-8 nm. Firstly, P25 powders are dissolved in NaOH solution under hydrothermal conditions, forming sodium titanate (Na2Ti3O7) intermediate precursor phase. Then, H2Ti3O7 is successfully obtained by ion exchange through acid washing from Na2Ti3O7 via an alkaline hydrothermal treatment. After calcination at 450 °C, the H2Ti3O7 is converted to a TiO2-B phase. At 600 °C, another anatase phase coexists with TiO2-B, which completely converts into anatase when annealed at 750 °C. Mesoporous TiO2-B nanobelts obtained after annealing at 450 °C are uniform with up to a few micrometers in length, 50-120 nm in width, and 5-15 nm in thickness. The resulting mesoporous TiO2-B nanobelts exhibit efficient H2 evolution capability, which is almost three times that of anatase TiO2 nanobelts.

Metal-Organic Frameworks and Their Derived Materials: Emerging Catalysts for a Sulfate Radicals-Based Advanced Oxidation Process in Water Purification.

With the ever-growing environmental issues, sulfate radical (SO4•- )-based advanced oxidation processes (SR-AOPs) have been attracting widespread attention due to their high selectivity and oxidative potential in water purification. Among various methods generating SO4•- , employing heterogeneous catalysts for activation of peroxymonosulfate or persulfate has been demonstrated as an effective strategy. Therefore, the future advances of SR-AOPs depend on the development of adequate catalysts with high activity and stability. Metal-organic frameworks (MOFs) with large surface area, ultrahigh porosity, and diversity of material design have been extensively used in heterogeneous catalysts, and more recently, enormous effort has been made to utilize MOFs-based materials for SR-AOPs applications. In this work, the state-of-the-art research on pristine MOFs, MOFs composites, and their derivatives, such as oxides, metal/carbon hybrids, and carbon materials for SR-AOPs, is summarized. The mechanisms, including radical and nonradical pathways, are also detailed in the discussion. This work will hopefully promote the future development of MOFs-based materials toward SR-AOPs applications.

Fabrication of Nanoporous Carbon Materials with Hard- and Soft-Templating Approaches: A Review.

Hard- and soft-templating approaches are one of potential strategies for the fabrication of functional nanoporous carbon materials with desired morphologies and properties. Enormous efforts have been paid for understanding the synthetic mechanisms that strongly influence the materials design and applications. All of these investigations are crucial to encourage the application of hard- and soft-templating approaches for the precise synthesis of nanoporous carbon materials. In this review, we mainly summarize significant works employing different synthetic methods for making carbon materials with various pore sizes and functionalities. The content of the review article contains: (i) Hard-templating synthesis of microporous carbon from zeolites; (ii) Hard-templating synthesis of mesoporous carbon from mesoporous silica; (iii) Hard-templating synthesis of macroporous carbon; and (iv) Soft-templating synthesis of mesoporous carbon. This review aims to provide a detailed glimpse of hard- and soft-templating approaches for future development of functional nanoporous carbon materials.

Biomolecule-Assisted Synthesis of Hierarchical Multilayered Boehmite and Alumina Nanosheets for Enhanced Molybdenum Adsorption.

The effective utilization of various biomolecules for creating a series of mesoporous boehmite (γ-AlOOH) and gamma-alumina (γ-Al2 O3 ) nanosheets with unique hierarchical multilayered structures is demonstrated. The nature and concentration of the biomolecules strongly influence the degree of the crystallinity, the morphology, and the textural properties of the resulting γ-AlOOH and γ-Al2 O3 nanosheets, allowing for easy tuning. The hierarchical γ-AlOOH and γ-Al2 O3 multilayered nanosheets synthesized by using biomolecules exhibit enhanced crystallinity, improved particle separation, and well-defined multilayered structures compared to those obtained without biomolecules. More impressively, these γ-AlOOH and γ-Al2 O3 nanosheets possess high surface areas up to 425 and 371 m2 g-1 , respectively, due to their mesoporous nature and hierarchical multilayered structure. When employed for molybdenum adsorption toward medical radioisotope production, the hierarchical γ-Al2 O3 multilayered nanosheets exhibit Mo adsorption capacities of 33.1-40.8 mg g-1 . The Mo adsorption performance of these materials is influenced by the synergistic combination of the crystallinity, the surface area, and the pore volume. It is expected that the proposed biomolecule-assisted strategy may be expanded for the creation of other 3D mesoporous oxides in the future.

Standing Mesochannels: Mesoporous PdCu Films with Vertically Aligned Mesochannels from Nonionic Micellar Solutions.

Mesoporous bimetallic palladium (Pd) alloy films with mesochannels perpendicularly aligned to the substrate are expected to show superior electrocatalytic activity and stability. The perpendicular mesochannels allow small molecules to efficiently access the active sites located not only at the surface but also within the film because of low diffusion resistance. When compared to pure Pd films, alloying with a secondary metal such as copper (Cu) is cost-effective and promotes resistance against adventitious poisoning through intermediate reactions known to impair the electrocatalytic performance. Here, we report the synthesis of mesoporous PdCu films by electrochemical deposition in nonionic micellar solutions. The mesoporous structures are vertically aligned on the substrate, and the final content of Pd and Cu can be adjusted by tuning the initial precursor molar ratio in the electrolyte solution.

Nanoarchitectured Graphene-Organic Frameworks (GOFs): Synthetic Strategies, Properties, and Applications.

Graphene-organic frameworks (GOFs) is a new class of graphene-based materials in which structure and properties can be designed by controlling the length and concentration of organic ligands, comparable to their tunable metal-organic frameworks (MOFs) counterpart. The structural properties (e.g., surface area, pore volume) and physico-chemical properties (e.g., electronic, thermal, and mechanical) of GOFs can be tuned based on the synthetic conditions. Such GOFs are promising as the next generation of novel materials for a wide range of potential applications such as H2 storage, electronic devices, sensors, drug carriers, etc. Here we report a review summarizing synthetic strategies, properties, and applications of GOFs.

Electrochemical Synthesis of Mesoporous Au-Cu Alloy Films with Vertically Oriented Mesochannels Using Block Copolymer Micelles.

We synthesized Au-Cu bimetallic alloy films with a controlled mesoporous architecture through electrochemical deposition using an electrolyte solution containing spherical polymeric micelles. The composition of the alloy films can be easily controlled by tuning the ratio between the Au and Cu species present in the electrolyte solution. At low Cu content, cage-type mesopores are formed, reflecting the parent micellar template. Surprisingly, upon increasing the Cu content, the cage-type mesopores fuse to form vertically aligned one-dimensional mesochannels. The vertical alignment of these mesopores is favorable for enhanced mass and ion transfer within the channels due to low diffusion resistance. The atomic distribution of Au and Cu is uniform over the entire film and free of any phase segregation. The as-synthesized mesoporous Au-Cu films exhibit excellent performance as a nonenzymatic glucose sensor with high sensitivity and selectivity, and the current response is linear over a wide range of concentrations. This work identifies the properties responsible for the promising performance of such mesoporous alloy films for the clinical diagnosis of diabetes. This micelle-assisted electrodeposition approach has a high degree of flexibility and can be simply extended from monometallic compounds to a multimetallic system, enabling the fabrication of various mesoporous alloy films suitable for different applications.

Electrochemical Deposition: An Advanced Approach for Templated Synthesis of Nanoporous Metal Architectures.

Well-constructed porous materials take an essential role in a wide range of applications, including energy conversion and storage systems, electrocatalysis, photocatalysis, and sensing. Although the tailored design of various nanoarchitectures has made substantial progress, simpler preparation methods are compelled to meet large-scale production requirements. Recently, advanced electrochemical deposition techniques have had a significant impact in terms of precise control upon the nanoporous architecture (i.e., pore size, surface area, pore structure, etc.), enabling access to a wide range of compositions. In this Account, we showcase the uniqueness of electrochemical deposition techniques, detail their implementation toward the synthesis of novel nanoporous metals, and finally outline the future research directions. Nanoporous metallic structures are attractive in that they can provide high surface area and large pore volume, easing mass transport of reactants and providing high accessibility to catalytically active metal surface. The great merit of the electrochemical deposition approach does not only lie in its versatility, being applicable to a wide range of compositions, but also in the nanoscale precision it affords when it comes to crystal growth control, which cannot be easily achieved by other bottom-up or top-down approaches. In this Account, we describe the significant progress made in the field of nanoporous metal designed through electrochemical deposition approaches using hard templates (i.e., porous silica, 3D templates of polymer and silica colloids) and soft templates (i.e., lyotropic liquid crystals, polymeric micelles). In addition, we will point out how it accounts for precise control over the crystal growth and describe the unique physical and chemical properties emerging from these novel materials. Up to date, our group has reported the synthesis of several nanoporous metals and alloys (e.g., Cu, Ru, Rh, Pd, Pt, Au, and their corresponding alloys) under various conditions through electrochemical deposition, while investigating their various potential applications. The orientation of the channel structure, the composition, and the nanoporosity can be easily controlled by selecting the appropriate surfactants or block copolymers. The inherent properties of the final product, such as framework crystallinity, catalytic activity, and resistance to oxidation, are depending on both the composition and pore structure, which in turn require suitable electrochemical conditions. This Account is divided into three main sections: (i) a history of electrochemical deposition using hard and soft templates, (ii) a description of the important mechanisms involved in the preparation of nanoporous materials, and (iii) a conclusion and future perspectives. We believe that this Account will promote a deeper understanding of the synthesis of nanoporous metals using electrochemical deposition methods, thus enabling new pathways to control nanoporous architectures and optimize their performance toward promising applications such as catalysis, energy storage, sensors, and so forth.