A soft touch with electron beams: Digging out structural information of nanomaterials with advanced scanning low energy electron microscopy coupled with deep learning.

Nanostructured materials continue to find applications in various electronic and sensing devices, chromatography, separations, drug delivery, renewable energy, and catalysis. While major advancements on the synthesis and characterization of these materials have already been made, getting information about their structures at sub-nanometer resolution remains challenging. It is also unfortunate to find that many emerging or already available powerful analytical methods take time to be fully adopted for characterization of various nanomaterials. The scanning low energy electron microscopy (SLEEM) is a good example to this. In this report, we show how clearer structural and surface information at nanoscale can be obtained by SLEEM, coupled with deep learning. The method is demonstrated using Au nanoparticles-loaded mesoporous silica as a model system. Moreover, unlike conventional scanning electron microscopy (SEM), SLEEM does not require the samples to be coated with conductive films for analysis; thus, not only it is convenient to use but it also does not give artifacts. The results further reveal that SLEEM and deep learning can serve as great tools to analyze materials at nanoscale well. The biggest advantage of the presented method is its availability, as most modern SEMs are able to operate at low energies and deep learning methods are already being widely used in many fields.

Ball Milling of La2O3 Tailors the Crystal Structure, Reactive Oxygen Species, and Free Radical and Non-Free Radical Photocatalytic Pathways.

Non-free radical photocatalysis with metal oxide catalysts is an important advanced oxidation process that enables the removal of various emerging environmental pollutants, such as tetracycline. Here, four hexagonal La2O3 photocatalysts with different densities of oxygen vacancy and crystalline features are synthesized and then further treated by ball milling. Ball milling of these La2O3 photocatalysts is found to increase the amount of oxygen vacancies on their surfaces and thereby the amount of 1O2 species produced by them. The photocatalytic degradation of TC by these La2O3 photocatalysts depends on the oxygen vacancies present on them. Furthermore, the ones with a strong (101) diffraction peak remove tetracycline from water systems largely with 1O2 and •OH species, whereas those with a weak (101) diffraction peak do so mainly via 1O2 and direct electron transfer (DET) process. Their overall catalytic properties are also studied by density functional theory calculations. Moreover, the organic products produced from tetracycline by La2O3 photocatalysts containing a strong (101) diffraction peak are found to be less toxic than those produced by La2O3 photocatalysts containing a weak (101) diffraction peak. This study also provides convincing evidence that the structures of La2O3 determine the species that is produced by it and that end up mediating photocatalytic reaction pathways (i.e., free radical versus non-free radical) to degrade an emerging environment pollutant.

Novel anionic surfactant-modified chlorhexidine and its potent antimicrobial properties.

Chlorhexidine dodecyl sulfate (CHX-DS) was synthesized and characterized via single-crystal X-ray diffraction (SC-XRD), 1H nuclear magnetic resonance (NMR) spectroscopy, 1H nuclear Overhauser effect spectroscopy (NOESY), and attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR). The solid-state structure, comprising a 1 : 2 stoichiometric ratio of chlorhexidine cations [C22H30Cl2N10]2+ to dodecyl sulfate anions [C12H25SO4]-, is the first report of chlorhexidine isolated with a surfactant. CHX-DS exhibits broad-spectrum antibacterial activity and demonstrates superior efficacy for reducing bacteria-generated volatile sulfur compounds (VSCs) as compared to chlorhexidine gluconate (CHG). The minimum inhibitory concentrations (MICs) of CHX-DS were 7.5, 2.5, 2.5, and 10 µM for S. enterica, E. coli, S. aureus, and S. mutans, respectively. Furthermore, MIC assays for E. coli and S. mutans demonstrate that CHX-DS and CHX exhibit a statistically significant efficacy enhancement in 2.5 µM treatment as compared to CHG. CHX-DS was incorporated into SBA-15, a mesoporous silica nanoparticle (MSN) framework, and its release was qualitatively measured via UV-vis in aqueous media, which suggests its potential as an advanced functional material for drug delivery applications.

Enhancing the electrocatalytic activities of metal organic frameworks for the oxygen evolution reaction with bimetallic groups.

Controlling the ratio of metals in bimetallic organic frameworks (MOFs) can not only alter the structures but also tailor the properties of MOFs. Herein, we report a series of electrocatalytically active CoxNiy-based bimetallic MOFs that are synthesized with the 3,5-pyridinedicarboxylic acid (3,5-H2pdc) ligand (where x : y = 20 : 1, 15 : 1, 10 : 1, 5 : 1, 1 : 1, and 1 : 20) and a facile, scalable, low temperature synthetic route. The materials have one-dimensional (1D), rod-like microstructures with different aspect ratios. While they all electrocatalyze the oxygen evolution reaction (OER) in alkaline solution (1 M KOH), their electrocatalytic performances vary substantially depending on their compositions. The CoxNiy-MOF with an optimal ratio of x : y = 15 : 1 (Co15Ni1-MOF) electrocatalyzes the OER with the highest maximum current density (92.2 mA cm-2 at 1.75 V vs. RHE) and the smallest overpotential (384 mV vs. RHE at 10 mA cm-2) in a 1 M KOH solution. It is also stable under constant current application during the electrocatalytic OER. This work demonstrates the application of bimetallic MOFs that are synthesized following a simple, low temperature synthetic route for the OER and their tailorable electrocatalytic properties for the OER by varying the ratio of two metals and the synthetic conditions used to produce them.

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.

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.

Incorporation of Bismuth Increases the Electrocatalytic Activity of Cobalt Borates for Oxygen Evolution Reaction.

The development of durable and efficient electrocatalysts composed of low-cost, earth-abundant metals for the oxygen evolution reaction (OER) is crucial for industrial-scale water splitting to produce green hydrogen on a large scale. Transition metal borates are considered good candidate electrocatalysts for OER due to their low cost, ease of synthesis, and good catalytic activity. In this work, we demonstrate that the incorporation of an oxophilic main group metal, bismuth (Bi), into cobalt borates produces highly effective electrocatalysts for OER. We also show that the catalytic activity of Bi-doped cobalt borates can be improved further by pyrolyzing them in an argon atmosphere. During pyrolysis, the Bi crystallites formed in the materials melt, transform into amorphous phases, interact better with the Co or B atoms in there, and form more synergistic catalytic sites for OER. By varying the amount of Bi as well as the pyrolysis temperature, different Bi-doped cobalt borates are synthesized, and the most optimal OER electrocatalyst is identified. Among them, the one with Co : Bi ratio of 9 : 1 and that is pyrolyzed at 450 °C exhibits the best catalytic activity, driving the reaction at a current density of 10 mA cm-2 with the lowest overpotential (318 mV) and a Tafel slope of 37 mV dec-1 .

Repurposing Anthelmintics: Rafoxanide- and Copper-Functionalized SBA-15 Carriers against Methicillin-Resistant Staphylococcus aureus.

The development of materials that can more efficiently administer antimicrobial agents in a controlled manner is urgently needed due to the rise in microbial resistance to traditional antibiotics. While new classes of antibiotics are developed and put into widespread usage, existing, inexpensive compounds can be repurposed to fight bacterial infections. Here, we present the synthesis of amine-functionalized SBA-15 mesoporous silica nanomaterials with physisorbed rafoxanide (RFX), a commonly used salicylanilide anthelmintic, and anchored Cu(II) ions that exhibit enhanced antimicrobial efficacy against the pathogenic bacterium Staphylococcus aureus. The synthesized nanomaterials are structurally characterized by a combination of physicochemical, thermal, and optical methods. Additionally, release studies are carried out in vitro to determine the effects of pH and the synthetic sequence used to produce the materials on Cu(II) ion release. Our results indicate that SBA-15 mesoporous silica nanocarriers loaded with Cu(II) and RFX exhibit 10 times as much bactericidal action against wild-type S. aureus as the nanocarrier loaded with only RFX. Furthermore, the synthetic sequence used to produce the nanomaterials could significantly affect (enhance) their bactericidal efficacy.

Hierarchically Ordered Nanoporous Carbon with Exclusively Surface-Anchored Cobalt as Efficient Electrocatalyst.

A hierarchically ordered porous carbon electrocatalyst with exclusively surface-anchored cobalt species, dubbed Co@HOPC, is synthesized from polyaniline and cobalt-functionalized silica microparticles templates, and its high electrocatalytic activity for the oxygen evolution reaction (OER) is demonstrated. The material requires a small potential (320 mV) to drive the reaction with a current density of 10 mA cm-2 and a small Tafel slope of 31.2 mV dec-1 . Moreover, Co@HOPC shows better catalytic activity for OER than in situ cobalt-doped and surface cobalt-loaded hierarchically ordered porous carbon materials synthesized by traditional methods. This is due to the abundant surface cobalt species present in Co@HOPC and the material's good electrical conductivity. This work provides a new strategy to utilize functionalized silica microparticles as templates to synthesize hierarchically ordered porous carbon materials with metal-rich surfaces and efficient electrocatalytic activities.

Metal-Functionalized Hydrogels as Efficient Oxygen Evolution Electrocatalysts.

Conductive polymer hydrogels have large surface areas and electrical conductivities. Their properties can be further tailored by functionalizing them with metals and nonmetals. However, the potential applications of metal-functionalized hydrogels for electrocatalysis have rarely been investigated. In this work, we report the synthesis of transition-metal-functionalized polyaniline-phytic acid (PANI-PA) hydrogels that show efficient electrocatalytic activities for the oxygen evolution reaction (OER). Among the many transition metals studied, Fe is accommodated by the hydrogel the most due to the favorable affinity of the PA groups in the hydrogel for Fe. Meanwhile, those containing both Fe and Co are found to be the most effective electrocatalysts for OER. The most optimized such hydrogel, NF@Hgel-Fe0.3Co0.1, which is made using a solution that has a 3:1 ratio of Fe and Co, needs an overpotential of only 280 mV to catalyze OER in 1 M KOH solution with a current density of 10 mV cm-2. Furthermore, these metal-functionalized PANI-PA hydrogels can easily be loaded on the nickel foam or carbon cloth via a simple soak-and-dry method to generate free-standing electrodes. Overall, this work demonstrates a facile synthesis and fabrication of sustainable and efficient OER electrocatalysts and electrodes that are composed of easily processable hydrogels functionalized with earth-abundant transition metals.

Highly Dispersed Mo2 C Nanodots in Carbon Nanocages Derived from Mo-Based Xerogel: Efficient Electrocatalysts for Hydrogen Evolution.

The production of hydrogen via electrochemical water splitting has the potential to enable the utilization of hydrogen-powered fuel cells on a large scale. However, to realize this technology, inexpensive, noble metal-free electrocatalysts possessing high performances for the hydrogen evolution reaction (HER) are needed. Mo2 C nanoparticles recently receive much attention as alternative noble metal-free electrocatalysts because their electronic structures are akin to that of Pt. However, the synthesis of Mo2 C at nanoscale with high catalytic activity for HER remains a great challenge. Moreover, although efforts have been made to prevent their aggregation, the particles coalesce during high temperature carbonization, which is typically used to produce such transition metal carbides. Here, the synthesis of Mo2 C nanodots that are well-dispersed within 3D cage-like carbon microparticles using rationally designed Mo-based xerogels, which are prepared via the sol-gel process as precursors, is reported. During their pyrolysis, the xerogels maintain their structures while the Mo species in them transform into well-dispersed Mo2 C nanodots in situ. The as-synthesized Mo2 C nanodots exhibit excellent electrocatalytic activity for HER, in both alkaline and acidic media, while remaining largely stable. The work also demonstrates a promising synthetic route and procedure to other well-dispersed yet stable nanocatalysts.

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.

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.

Cetylpyridinium Trichlorostannate: Synthesis, Antimicrobial Properties, and Controlled-Release Properties via Electrical Resistance Tomography.

Cetylpyridinium trichlorostannate (CPC-Sn), comprising cetylpyridinium chloride (CPC) and stannous chloride, was synthesized and characterized via single-crystal X-ray diffraction measurements indicating stoichiometry of C21H38NSnCl3 where the molecules are arranged in a 1:1 ratio with a cetylpyridinium cation and a [SnCl3]- anion. CPC-Sn has shown potential for application as a broad-spectrum antimicrobial agent, to reduce bacteria-generated volatile sulfur compounds and to produce advanced functional materials. In order to investigate its controlled-release properties, electrical resistance tomography was implemented. The results demonstrate that CPC-Sn exhibits extended-release properties in an aqueous environment as opposed to the CPC counterpart.

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.

Active Site Engineering in Porous Electrocatalysts.

Electrocatalysis is at the center of many sustainable energy conversion technologies that are being developed to reduce the dependence on fossil fuels. The past decade has witnessed significant progresses in the exploitation of advanced electrocatalysts for diverse electrochemical reactions involved in electrolyzers and fuel cells, such as the hydrogen evolution reaction (HER), the oxygen reduction reaction (ORR), the CO2 reduction reaction (CO2 RR), the nitrogen reduction reaction (NRR), and the oxygen evolution reaction (OER). Herein, the recent research advances made in porous electrocatalysts for these five important reactions are reviewed. In the discussions, an attempt is made to highlight the advantages of porous electrocatalysts in multiobjective optimization of surface active sites including not only their density and accessibility but also their intrinsic activity. First, the current knowledge about electrocatalytic active sites is briefly summarized. Then, the electrocatalytic mechanisms of the five above-mentioned reactions (HER, ORR, CO2 RR, NRR, and OER), the current challenges faced by these reactions, and the recent efforts to meet these challenges using porous electrocatalysts are examined. Finally, the future research directions on porous electrocatalysts including synthetic strategies leading to these materials, insights into their active sites, and the standardized tests and the performance requirements involved are discussed.

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.

Synthesis, Characterization, and Investigation of the Antimicrobial Activity of Cetylpyridinium Tetrachlorozincate.

Cetylpyridinium tetrachlorozincate (referred to herein as (CP)2ZnCl4) was synthesized and its solid-state structure was elucidated via single-crystal X-ray diffraction (SC-XRD), revealing a stoichiometry of C42H76Cl4N2Zn with two cetylpyridinium (CP) cations per [ZnCl4]2- tetrahedra. Crystal structures at 100 and 298 K exhibited a zig-zag pattern with alternating alkyl chains and zinc units. The material showed potential for application as a broad-spectrum antimicrobial agent, to reduce volatile sulfur compounds (VSCs) generated by bacteria, and in the fabrication of advanced functional materials. Minimum inhibitory concentration (MIC) of (CP)2ZnCl4 was 60, 6, and 6 µg mL-1 for Salmonella enterica, Staphylococcus aureus, and Streptococcus mutans, respectively. The MIC values of (CP)2ZnCl4 were comparable to that of pure cetylpyridinium chloride (CPC), despite the fact that approximately 16% of the bactericidal CPC is replaced with bacteriostatic ZnCl2 in the structure. A modified layer-by-layer deposition technique was implemented to synthesize mesoporous silica (i.e., SBA-15) loaded with approximately 9.0 wt % CPC and 8.9 wt % Zn.