High Density Single Fe Atoms on Mesoporous N-Doped Carbons: Noble Metal-Free Electrocatalysts for Oxygen Reduction Reaction in Acidic and Alkaline Media.

It remains a challenge to develop efficient noble metal-free electrocatalysts for the oxygen reduction reaction (ORR) in various renewable energy systems. Single atom catalysts have recently drawn great attention as promising candidates both due to their high activity and their utmost atom utilization for electrocatalytic ORR. Herein, the synthesis of an efficient ORR electrocatalyst that is composed of N-doped mesoporous carbon and a high density (4.05 wt%) of single Fe atoms via pyrolysis Fe-conjugated polymer is reported. Benefiting from the abundant atomic Fe-N4 sites on its conductive, mesoporous carbon structures, this material exhibits an excellent electrocatalytic activity for ORR, with positive onset potentials of 0.93 and 0.98 V in acidic and alkaline media, respectively. Its electrocatalytic performance for ORR is also comparable to that of Pt/C (20 wt%) in both media. Furthermore, it electrocatalyzes the reaction almost fully to H2 O (or barely to H2 O2 ). Additionally, it is durable and tolerates the methanol crossover reaction well. Furthermore, a proton exchange membrane fuel cell and a zinc-air battery assembled using it on their cathode deliver high maximum power densities (320 and 91 mW cm-2 , respectively). Density functional theory calculation reveals that the material's decent electrocatalytic performance for ORR is due to its atomically dispersed Fe-N4 sites.

Nanomaterials for Removal of Phenolic Derivatives from Water Systems: Progress and Future Outlooks.

Environmental pollution remains one of the most challenging problems facing society worldwide. Much of the problem has been caused by human activities and increased usage of various useful chemical agents that inadvertently find their way into the environment. Triclosan (TCS) and related phenolic compounds and derivatives belong to one class of such chemical agents. In this work, we provide a mini review of these emerging pollutants and an outlook on the state-of-the-art in nanostructured adsorbents and photocatalysts, especially nanostructured materials, that are being developed to address the problems associated with these environmental pollutants worldwide. Of note, the unique properties, structures, and compositions of mesoporous nanomaterials for the removal and decontamination of phenolic compounds and derivatives are discussed. These materials have a great ability to scavenge, adsorb, and even photocatalyze the decomposition of these compounds to mitigate/prevent their possible harmful effects on the environment. By designing and synthesizing them using silica and titania, which are easier to produce, effective adsorbents and photocatalysts that can mitigate the problems caused by TCS and its related phenolic derivatives in the environment could be fabricated. These topics, along with the authors' remarks, are also discussed in this review.

Nanostructured Carbon Electrocatalysts for Energy Conversions.

The growing energy demand worldwide has led to increased use of fossil fuels. This, in turn, is making fossil fuels dwindle faster and cause more negative environmental impacts. Thus, alternative, environmentally friendly energy sources such as fuel cells and electrolyzers are being developed. While significant progress has already been made in this area, such energy systems are still hard to scale up because of their noble metal catalysts. In this concept paper, first, various scalable nanocarbon-based electrocatalysts that are being synthesized for energy conversions in these energy systems are introduced. Next, notable heteroatom-doping and nanostructuring strategies that are applied to produce different nanostructured carbon materials with high electrocatalytic activities for energy conversions are discussed. The concepts used to develop such materials with different structures and large density of dopant-based catalytic functional groups in a sustainable way, and the challenges therein, are emphasized in the discussions. The discussions also include the importance of various analytical, theoretical, and computational methods to probe the relationships between the compositions, structures, dopants, and active catalytic sites in such materials. These studies, coupled with experimental studies, can further guide innovative synthetic routes to efficient nanostructured carbon electrocatalysts for practical, large-scale energy conversion applications.

Single Co-Atoms as Electrocatalysts for Efficient Hydrazine Oxidation Reaction.

Single-atom catalysts (SACs) have aroused great attention due to their high atom efficiency and unprecedented catalytic properties. A remaining challenge is to anchor the single atoms individually on support materials via strong interactions. Herein, single atom Co sites have been developed on functionalized graphene by taking advantage of the strong interaction between Co2+ ions and the nitrile group of cyanographene. The potential of the material, which is named G(CN)Co, as a SAC is demonstrated using the electrocatalytic hydrazine oxidation reaction (HzOR). The material exhibits excellent catalytic activity for HzOR, driving the reaction with low overpotential and high current density while remaining stable during long reaction times. Thus, this material can be a promising alternative to conventional noble metal-based catalysts that are currently widely used in HzOR-based fuel cells. Density functional theory calculations of the reaction mechanism over the material reveal that the Co(II) sites on G(CN)Co can efficiently interact with hydrazine molecules and promote the NH bond-dissociation steps involved in the HzOR.

Antimicrobial properties of novel ionic liquids derived from imidazolium cation with phenolic functional groups.

Bacterial infections are nowadays among the major threats to public health worldwide. Thus, there is an urgent and increased need for new antimicrobial agents. As a result, the exploration of the antimicrobial properties of different substances including ionic liquids (ILs) has recently attracted great attention. The present work is aimed at evaluating how the addition of halogens and hydrophobic substituents on alkylimidazolium units of ILs as well as the increase in their chain lengths affects the antimicrobial properties of such ILs. After their synthesis, the antibacterial activities of these compounds against Pseudomona aeruginosa, Escherichia coli, and Staphylococcus aureus are determined by measuring their minimal inhibitory concentrations (MICs). Key features in ILs-membrane interactions are also studied using long-term all-atom molecular dynamics simulations (MDs). The results show that these ILs have good antibacterial activity against S. aureus, E. coli, and P. aeruginosa, with MIC values range from <7.81 to 62.50 µM. The antimicrobial property of tert-butyl N-methylphenolimidazolium salts (denoted as 8b and 8c) is particularly better with MIC values of < 7.81 µM. The antibacterial efficacy is also found to depend on the alkyl chain length and substituents on the phenolic ring. Finally, MDs done for ILs in a phosphatidylcholine (POPC) bilayer show key features in the mechanism of IL-induced membrane disruption, where the ILs are inserted as clusters into one side of the bilayer until saturation is reached. This insertion increases "leaflet strain" up to critical threshold, likely triggering the morphological disruption of the membranes in the microbes.

Nonprecious Bimetallic Sites Coordinated on N-Doped Carbons with Efficient and Durable Catalytic Activity for Oxygen Reduction.

Developing efficient, inexpensive, and durable electrocatalysts for the oxygen reduction reaction (ORR) is important for the large-scale commercialization of fuel cells and metal-air batteries. Herein, a hierarchically porous bimetallic Fe/Co single-atom-coordinated N-doped carbon (Fe/Co-Nx -C) electrocatalyst for ORR is synthesized from Fe/Co-coordinated polyporphyrin using silica template-assisted and silica-protection synthetic strategies. In the synthesis, first silica nanoparticles-embedded, silica-protected Fe/Co-polyporphyrin is prepared. It is then pyrolyzed and treated with acidic solution. The resulting Fe/Co-Nx -C material has a large specific surface area, large electrochemically active surface area, good conductivity, and catalytically active Fe/Co-Nx sites. The material exhibits a very good electrocatalytic activity for the ORR in alkaline media, with a half-wave potential of 0.86 V versus reversible hydrogen electrode, which is better than that of Pt/C (20 wt%). Furthermore, it shows an outstanding operational stability and durability during the reaction. A zinc-air battery (ZAB) assembled using Fe/Co-Nx -C as an air-cathode electrocatalyst gives a high peak power density (152.0 mW cm-2 ) and shows a good recovery property. Furthermore, the performance of the battery is better than a corresponding ZAB containing Pt/C as an electrocatalyst. The work also demonstrates a synthetic route to a highly active, stable, and scalable single-atom electrocatalyst for ORR in ZABs.

Optimization of Active Sites via Crystal Phase, Composition, and Morphology for Efficient Low-Iridium Oxygen Evolution Catalysts.

Reducing the amount of iridium in oxygen evolution electrocatalysts without compromising their catalytic performances is one of the major requirements in proton-exchange-membrane water electrolyzers. Herein, with the help of theoretical studies, we show that anatase-type TiO2 -IrO2 solid solutions possess more active iridium catalytic sites for the oxygen evolution reaction (OER) than IrO2 , the benchmark OER catalyst. Note that the same is not observed for their rutile-type counterparts. However, owing to their thermodynamic metastability, anatase-type TiO2 -IrO2 solid solutions are generally hard to synthesize. Our theoretical studies demonstrate that such catalytically active anatase-type solid-solution phases can be created in situ on the surfaces of readily available SrTiO3 -SrIrO3 solid solutions during electrocatalysis in acidic solution as the solution can etch away Sr atoms. We experimentally show this with porous SrTiO3 -SrIrO3 solid-solution nanotubes synthesized by a facile synthetic route that contain 56 % less iridium than IrO2 yet show an order of magnitude higher apparent catalytic activity for OER in acidic solution.

A Blinking Mesoporous TiO2-x Composed of Nanosized Anatase with Unusually Long-Lived Trapped Charge Carriers.

A mesoporous TiO2-x material comprised of small, crystalline, vacancy-rich anatase nanoparticles (NPs) shows unique optical, thermal, and electronic properties. It is synthesized using polymer-derived mesoporous carbon (PDMC) as a template. The PDMC pores serve as physical barriers during the condensation and pyrolysis of a titania precursor, preventing the titania NPs from growing beyond 10 nm in size. Unlike most titania nanomaterials, during pyrolysis the NPs undergo no transition from the anatase to rutile phase and they become catalytically active reduced TiO2-x . When exposed to a slow electron beam, the NPs exhibit a charge/discharge behavior, lighting up and fading away for an average period of 15 s for an extended period of time. The NPs also show a 50 nm red-shift in their UV/Vis absorption and long-lived charge carriers (electrons and holes) at room temperature in the dark, even long after UV irradiation. The NPs as photocatalysts show a good activity for CO2 reduction.

One-Pot Hydrothermal Synthesis of Benzalkonium-Templated Mesostructured Silica Antibacterial Agents.

Novel mesostructured silica microparticles are synthesized, characterized, and investigated as a drug delivery system (DDS) for antimicrobial applications. The materials exhibit a relatively high density (0.56 g per 1 g SiO2) of benzalkonium chloride (BAC), pore channels of 18 Å in width, and a high surface area (1500 m2/g). Comparison of the small-angle X-ray diffraction (SAXRD) pattern with Barrett-Joyner-Halenda (BJH) pore size distribution data suggests that the 18 Å pores exhibit short-range ordering and a wall thickness of ca. 12 Å. Drug release studies demonstrate pH-responsive controlled release of BAC without additional surface modification of the materials. Prolonged drug release data were analyzed using a power law (Korsmeyer-Peppas) model and indicate substantial differences in release mechanism in acidic (pH 4.0, 5.0, 6.5) versus neutral (pH 7.4) solutions. Microbiological assays demonstrate a significant time-dependent reduction in Staphylococcus aureus and Salmonella enterica viability above 10 and 130 mg L-1 of the synthesized materials, respectively. The viability of cells is reduced over time compared to control samples. The findings will help in widening the use of BAC as a disinfectant and bactericidal agent, especially in pharmaceutical and food industries where Gram-positive and Gram-negative bacterial contamination is common.

Cu and Cu-Based Nanoparticles: Synthesis and Applications in Catalysis.

The applications of copper (Cu) and Cu-based nanoparticles, which are based on the earth-abundant and inexpensive copper metal, have generated a great deal of interest in recent years, especially in the field of catalysis. The possible modification of the chemical and physical properties of these nanoparticles using different synthetic strategies and conditions and/or via postsynthetic chemical treatments has been largely responsible for the rapid growth of interest in these nanomaterials and their applications in catalysis. In addition, the design and development of novel support and/or multimetallic systems (e.g., alloys, etc.) has also made significant contributions to the field. In this comprehensive review, we report different synthetic approaches to Cu and Cu-based nanoparticles (metallic copper, copper oxides, and hybrid copper nanostructures) and copper nanoparticles immobilized into or supported on various support materials (SiO2, magnetic support materials, etc.), along with their applications in catalysis. The synthesis part discusses numerous preparative protocols for Cu and Cu-based nanoparticles, whereas the application sections describe their utility as catalysts, including electrocatalysis, photocatalysis, and gas-phase catalysis. We believe this critical appraisal will provide necessary background information to further advance the applications of Cu-based nanostructured materials in catalysis.

Highly Active, Nonprecious Electrocatalyst Comprising Borophene Subunits for the Hydrogen Evolution Reaction.

Developing nonprecious hydrogen evolution electrocatalysts that can work well at large current densities (e.g., at 1000 mA/cm2: a value that is relevant for practical, large-scale applications) is of great importance for realizing a viable water-splitting technology. Herein we present a combined theoretical and experimental study that leads to the identification of α-phase molybdenum diboride (α-MoB2) comprising borophene subunits as a noble metal-free, superefficient electrocatalyst for the hydrogen evolution reaction (HER). Our theoretical finding indicates, unlike the surfaces of Pt- and MoS2-based catalysts, those of α-MoB2 can maintain high catalytic activity for HER even at very high hydrogen coverage and attain a high density of efficient catalytic active sites. Experiments confirm α-MoB2 can deliver large current densities in the order of 1000 mA/cm2, and also has excellent catalytic stability during HER. The theoretical and experimental results show α-MoB2's catalytic activity, especially at large current densities, is due to its high conductivity, large density of efficient catalytic active sites and good mass transport property.

Hollow Mesoporous Carbon Microparticles and Micromotors with Single Holes Templated by Colloidal Silica-Assisted Gas Bubbles.

A simple, new synthetic method that produces hollow, mesoporous carbon microparticles, each with a single hole on its surface, is reported. The synthesis involves unique templates, which are composed of gaseous bubbles and colloidal silica, and poly(furfuryl alcohol) as a carbon precursor. The conditions that give these morphologically unique carbon microparticles are investigated, and the mechanisms that result in their unique structures are proposed. Notably, the amount of colloidal silica and the type of polymer are found to hugely dictate whether or not the synthesis results in hollow asymmetrical microparticles, each with a single hole. The potential application of the particles as self-propelled micromotors is demonstrated.

The role of electronic coupling between substrate and 2D MoS2 nanosheets in electrocatalytic production of hydrogen.

The excellent catalytic activity of metallic MoS2 edges for the hydrogen evolution reaction (HER) has led to substantial efforts towards increasing the edge concentration. The 2H basal plane is less active for the HER because it is less conducting and therefore possesses less efficient charge transfer kinetics. Here we show that the activity of the 2H basal planes of monolayer MoS2 nanosheets can be made comparable to state-of-the-art catalytic properties of metallic edges and the 1T phase by improving the electrical coupling between the substrate and the catalyst so that electron injection from the electrode and transport to the catalyst active site is facilitated. Phase-engineered low-resistance contacts on monolayer 2H-phase MoS2 basal plane lead to higher efficiency of charge injection in the nanosheets so that its intrinsic activity towards the HER can be measured. We demonstrate that onset potentials and Tafel slopes of ∼-0.1 V and ∼50 mV per decade can be achieved from 2H-phase catalysts where only the basal plane is exposed. We show that efficient charge injection and the presence of naturally occurring sulfur vacancies are responsible for the observed increase in catalytic activity of the 2H basal plane. Our results provide new insights into the role of contact resistance and charge transport on the performance of two-dimensional MoS2 nanosheet catalysts for the HER.

Metal-Free and Noble Metal-Free Heteroatom-Doped Nanostructured Carbons as Prospective Sustainable Electrocatalysts.

The large-scale deployment of many types of fuel cells and electrolyzers is currently constrained by the lack of sustainable and efficient catalysts that can replace the less earth-abundant, noble metal-based catalysts, which are commonly used in these renewable energy systems. This burgeoning issue has led to explosive research efforts worldwide to find alternative, metal-free and noble metal-free catalysts that are composed of inexpensive and earth-abundant elements. Hence, the recent discoveries that doping carbon nanomaterials with heteroatoms (such as N, S, B, etc.) can give sustainable materials with good electrocatalytic activity for reactions carried out in fuel cells and electrolyzers have been not only quite exciting but also very promising to address these challenging issues. Interestingly, even though they contain no metals or involve only the inexpensive, more earth-abundant ones, the catalytic activity of some of these materials fares well with those of the commercially used noble metal-based electrocatalysts, such as Pt/C. However, research efforts to improve the catalytic activity, selectivity, and stability of some of these materials for various reactions are still necessary and thus continuing. While some of these efforts have focused on finding synthetic methods that can tune the structures and compositions of already known materials and thereby improve their catalytic properties (activity, selectivity, stability, etc.), others have focused on developing entirely new materials that can exhibit better or superior catalytic properties. In these efforts, additional considerations are also being paid to find facile synthetic routes or renewable and inexpensive precursors that can lead to such types of catalysts in order to make the entire process highly sustainable and widely applicable. In this Account, notable heteroatom-doped carbon catalysts that have been developed for reactions in fuel cells and water electrolyzers, the various synthetic procedures employed to make them, and the challenges involved in their synthesis as well as their characterizations are discussed. The methods used to systematically vary the structures and compositions of the precursors of these materials, as well as the materials themselves, and the different experimental, imaging, and spectroscopic methods used to investigate the properties and structure-property relationships of the materials for various energy related reactions are also included. The discussions focus mainly around the recent notable results reported on these materials by the author's and other research groups worldwide, albeit not exhaustively. Finally, the author's perspective about the challenges remaining in the field that need to be addressed, the many existing unanswered questions that beg for more research, and the future prospects for research related to the above topics are also mentioned.

Heteroatom-Doped Carbon Materials for Electrocatalysis.

Fuel cells, water electrolyzers, and metal-air batteries are important energy systems that have started to play some roles in our renewable energy landscapes. However, despite much research works carried out on them, they have not yet found large-scale applications, mainly due to the unavailability of sustainable catalysts that can catalyze the reactions employed in them. Currently, noble metal-based materials are the ones that are commonly used as catalysts in most commercial fuel cells, electrolyzers, and metal-air batteries. Hence, there has been considerable research efforts worldwide to find alternative noble metal-free and metal-free catalysts composed of inexpensive, earth-abundant elements for use in the catalytic reactions employed in these energy systems. In this concept paper, a brief introduction on catalysis in renewable energy systems, followed by the recent efforts to develop sustainable, heteroatom-doped carbon and non-noble metal-based electrocatalysts, the challenges to unravel their structure-catalytic activity relationships, and the authors' perspectives on these topics and materials, are discussed.

Hierarchically Self-Assembled Star-Shaped ZnO Microparticles for Electrochemical Sensing of Amines.

Novel, hierarchically nanostructured, star-shaped ZnO (SSZ) microparticles are synthesized by a hydrothermal synthetic route. The SSZ microparticles serve as effective platforms for electrochemical detection of amines in solution. The morphology and structure of the materials are characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and UV/Vis spectroscopy. The as-synthesized SSZ microparticles comprise self-assembled hexagonal prisms that possess nanometer and micrometer pores in their structure and on their surfaces-structural features that are conducive to sensing applications. An electrode fabricated by using the hierarchically nanostructured SSZ materials serve as a sensitive electrochemical sensor for detection of low concentrations of ethylenediamine, with a sensitivity of 2.98×10(-2)  mA cm(-2)  mm(-1) , a detection limit of 2.36×10(-2)  mm, and a short response time of 8 s.

Core-shell nanoparticles: synthesis and applications in catalysis and electrocatalysis.

Core-shell nanoparticles (CSNs) are a class of nanostructured materials that have recently received increased attention owing to their interesting properties and broad range of applications in catalysis, biology, materials chemistry and sensors. By rationally tuning the cores as well as the shells of such materials, a range of core-shell nanoparticles can be produced with tailorable properties that can play important roles in various catalytic processes and offer sustainable solutions to current energy problems. Various synthetic methods for preparing different classes of CSNs, including the Stöber method, solvothermal method, one-pot synthetic method involving surfactants, etc., are briefly mentioned here. The roles of various classes of CSNs are exemplified for both catalytic and electrocatalytic applications, including oxidation, reduction, coupling reactions, etc.

In Situ Growth and Characterization of Metal Oxide Nanoparticles within Polyelectrolyte Membranes.

This study describes a novel approach for the in situ synthesis of metal oxide-polyelectrolyte nanocomposites formed via impregnation of hydrated polyelectrolyte films with binary water/alcohol solutions of metal salts and consecutive reactions that convert metal cations into oxide nanoparticles embedded within the polymer matrix. The method is demonstrated drawing on the example of Nafion membranes and a variety of metal oxides with an emphasis placed on zinc oxide. The in situ formation of nanoparticles is controlled by changing the solvent composition and conditions of synthesis that for the first time allows one to tailor not only the size, but also the nanoparticle shape, giving a preference to growth of a particular crystal facet. The high-resolution TEM, SEM/EDX, UV-vis and XRD studies confirmed the homogeneous distribution of crystalline nanoparticles of circa 4 nm and their aggregates of 10-20 nm. The produced nanocomposite films are flexible, mechanically robust and have a potential to be employed in sensing, optoelectronics and catalysis.

Unique Electronic Structure in a Porous Ga-In Bimetallic Oxide Nano-Photocatalyst with Atomically Thin Pore Walls.

A facile synthetic route is presented that produces a porous Ga-In bimetallic oxide nanophotocatalyst with atomically thin pore walls. The material has an unprecedented electronic structure arising from its ultrathin walls. The bottom of the conduction band and the top of the valence band of the material are distributed on two opposite surfaces separated with a small electrostatic potential difference. This not only shortens the distance by which the photogenerated charges travel from the sites where they are generated to the sites where they catalyze the reactions, but also facilitates charge separations in the material. The porous structure within the walls results in a large density of exposed surface reactive/catalytic sites. Because of these optimized electronic and surface structures, the material exhibits superior photocatalytic activity toward the hydrogen evolution reaction (HER).

High-index faceted Ni3S2 nanosheet arrays as highly active and ultrastable electrocatalysts for water splitting.

Elaborate design of highly active and stable catalysts from Earth-abundant elements has great potential to produce materials that can replace the noble-metal-based catalysts commonly used in a range of useful (electro)chemical processes. Here we report, for the first time, a synthetic method that leads to in situ growth of {2̅10} high-index faceted Ni3S2 nanosheet arrays on nickel foam (NF). We show that the resulting material, denoted Ni3S2/NF, can serve as a highly active, binder-free, bifunctional electrocatalyst for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Ni3S2/NF is found to give ∼100% Faradaic yield toward both HER and OER and to show remarkable catalytic stability (for >200 h). Experimental results and theoretical calculations indicate that Ni3S2/NF's excellent catalytic activity is mainly due to the synergistic catalytic effects produced in it by its nanosheet arrays and exposed {2̅10} high-index facets.