Substrate Selection for Fundamental Studies of Electrocatalysts and Photoelectrodes: Inert Potential Windows in Acidic, Neutral, and Basic Electrolyte
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bio-inspired↗
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Carbon nanotube switches for memory, RF communications and sensing applications, and methods of making the same
Switches having an in situ grown carbon nanotube as an element thereof, and methods of fabricating such switches. A carbon nanotube is grown in situ in mechanical connection with a conductive substrate, such as a heavily doped silicon wafer or an SOI wafer. The carbon nanotube is electrically connected at one location to a terminal. At another location of the carbon nanotube there is situated a pull electrode that can be used to elecrostatically displace the carbon nanotube so that it selectively makes contact with either the pull electrode or with a contact electrode. Connection to the pull electrode is sufficient to operate the device as a simple switch, while connection to a contact electrode is useful to operate the device in a manner analogous to a relay. In various embodiments, the devices disclosed are useful as at least switches for various signals, multi-state memory, computational devices, and multiplexers.
Kaul, Anupama B.↗
Cobalt-Based Nonprecious Metal Catalysts Derived from Metal–Organic Frameworks for High-Rate Hydrogenation of Carbon Dioxide
The development of cost-effective catalysts with both high activity and selectivity for carbon–oxygen bond activation is a major challenge and has important ramifications for making value-added chemicals from carbon dioxide (CO 2 ). Herein, we present a one-step pyrolysis of metal organic frameworks that yields highly dispersed cobalt nanoparticles embedded in a carbon matrix which shows exceptional catalytic activity in the reverse water gas shift reaction. Incorporation of nitrogen into the carbon-based supports resulted in increased reaction activity and selectivity toward carbon monoxide (CO), likely because of the formation of a Mott–Schottky interface. At 300 °C and a high space velocity of 300 000 mL g –1 h –1 , the catalyst exhibited a CO 2 conversion rate of 122 μmolCO 2 g –1 s –1 , eight times higher than that of a reference Cu/ZnO/Al 2 O 3 catalyst. Our experimental and computational results suggest that nitrogen-doping lowers the energy barrier for the formation of formate intermediates (CO 2 * + H* → COOH* + *), in addition to the redox mechanism (CO 2 * + * → CO* + O*). This enhancement is attributed to the efficient electron transfer at the cobalt–support interface, leading to higher hydrogenation activity and opening new avenues for the development of CO 2 conversion technology.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
CO (2) Electroreduction on Borated Copper Surfaces: Boron Active Sites, Not Copper
Boron-doped copper has recently emerged as an active and stable catalyst for the electrochemical reduction of CO 2 to value-added C 2 products. Here, in this work, we develop a realistic model of CO electroreduction on surface borides of copper under operational conditions, taking into account the effects of electrode potential, electrolyte environment, and pH. We study the possible reconstruction of the electrocatalyst surface using grand canonical DFT and global optimization to obtain a potential-dependent grand canonical ensemble description of metastable, hydrogen-covered catalyst surfaces. Two key surface configurations, low H coverage (LC, −0.6 V SHE ) and high H coverage (HC, −0.8 V SHE ), dominate this ensemble, with the former being kinetically persistent and C 2 selective under strongly reducing conditions. Nonmetallic boron sites on the surface copper boride are found to bind CO more strongly than copper sites, and mechanistic investigation of CO electroreduction pathways presents a surprisingly unconventional case of boron-centered reactivity in contrast to typical copper-centered reactivity. Neighboring boron sites present along boron chains on the surface copper boride are found to facilitate C−C coupling, thereby driving the high C 2 selectivity of this electrocatalyst.
boron-doped copper↗
Doping Effect of Fe Ions on the Structural, Electrical, and Magnetic Properties of SrTiO{sub 3} Nanoceramic Matrix
In the present investigation, strontium titanate nanoceramic was synthesized by incorporating iron (Fe) ion with general formula SrTi{sub 1−x}Fe{sub x}O{sub 3} (x = 0.0, 0.1, 0.2, and 0.4) using sol-gel autocombustion method. The effect of Fe ions on the structural, morphological, electrical, dielectric, and magnetic properties of the prepared matrix has been investigated by various characterization techniques with the appropriate formulation. The structural properties such as phase space, crystallite size (D), and lattice parameter (a) of prepared matrix are calculated by X-ray diffraction (XRD) technique. The functional groups were analyzed by Fourier transform infrared spectroscopy (FT-IR). The surface morphology of the prepared nanoceramic matrix has been determined by using field emission scanning electron microscopy (FE-SEM) analysis. Calculation of average particle size and diffraction patterns was confirmed by using images from transmission electron microscopy (TEM) and selected area electron diffraction pattern (SAED), respectively. An energy dispersive spectrum analysis (EDS) confirmed the compositional stoichiometry in the investigated matrix. Electrical conductivity increased the prepared sample due to the increasing in the Fe concentration and temperature. The dielectric parameters in the frequency range of 30 Hz to 1 MHz were found higher at lower frequencies. The pure SrTiO{sub 3} matrix shows a paramagnetic nature at room temperature, but for a higher concentration of Fe doping was used to observe the weak ferromagnetic nature. Therefore, due to Fe ion concentration, the properties of the prepared matrix have been completely varied and enhancement in the magnetic properties was observed.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Syntheses of gold supported on metal oxides and their application in organic transformations
Herein, we report a general and straightforward synthesis method for gold supported on mesoporous and microporous metal oxides. Supported materials, in general, show higher crystallinity compare to unsupported systems as verified through powder X-ray diffraction (XRD). Also, through XRD, most of the metal is observed to be in its oxide form, whereas the gold support was found to be in its metallic state, which has been further confirmed from TEM. In terms of surface area, the catalyst was not found to follow any trend. Morphology wise, there are no changes observed after doping except in few cases. Combined results from XRD, X-ray fluorescence spectroscopy, Auger, and X-ray photoelectron spectroscopy suggest that gold is mainly in the bulk and very little (0.04% in case of gold doped calcium oxide) or non (in case of gold doped mixed manganese-cerium oxide) on the surface. The presence of Au (0) 4f peaks in XPS further confirms the metallic state of the gold. Oxides of indium, magnesium and calcium have been studied for the organic transformation reactions. An enhancement in activity and product selectivity was observed in the case of the gold supported catalysts. Indium serves as a great catalyst for C–C coupling and electrophilic aromatic substitution reactions and gives >99% conversion. Interestingly, 88% selectivity for C–C coupling and >99% selectivity for aromatic substitution have been achieved at 100 °C and room temperature respectively. Magnesium and calcium give Knoevenagel condensation products. At room temperature with very low catalyst loading, >99% conversion and selectivity were observed for the Knoevenagel reaction with as high as 35.30 TOF. Finally, a mechanism for the C–C coupling reaction has been proposed based on these results.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Selective capture of radionuclides (U, Pu, Th, Am and Co) using functional nanoporous sorbents
Using our self-assembled silanol technology, we developed eight functional nanoporous silica sorbents for capturing two classes of radionuclides: the actinide uranium (U), thorium (Th), plutonium (Pu), americium (Am) and the transition metal cobalt (Co). We tested them in sea, ground, and river water that were adjusted to pH 0-8.0 and doped with competing metals (Mg, Ca, K, Se, Mn, Fe, Co, Cu, Zn, and Mo) at levels encountered in environmental or physiological samples. Sorbents having three analogs of hydroxypyridinones (HOPO) and acetamide phosphonate (Ac-Phos) were exceptional at capturing U, Th, and Pu from pH 2.0 to 8.0, and very good at capturing Am from pH 5.0 to 8.0 with the affinity ranged from 3,4-HOPO > 1,2-HOPO > 3,2-HOPO > Ac-Phos. However, the affinity is reversed at near zero pH. For capturing Co, a family of glycine derivatives on nanoporous silica has been developed and the affinity for Co ranged from IDAA ~ DE4A > ED3A between pH 5.0-8.0. Our materials significantly outperformed the commercially available cation sorbents such as Chelex-100 and activated carbon in terms of binding affinity and rate; thus demonstrating great potential to be used as decorporation agents for water treatment and recovery of valuable actinides.
uranium (U), thorium (Th), plutonium (Pu), americi↗
Dynamically Unveiling Metal–Nitrogen Coordination during Thermal Activation to Design High-Efficient Atomically Dispersed CoN 4 Active Sites
We elucidate the structural evolution of CoN 4 sites during thermal activation by developing a zeolitic imidazolate framework (ZIF)-8-derived carbon host as an ideal model for Co 2+ ion adsorption. Subsequent in situ X-ray absorption spectroscopy analysis can dynamically track the conversion from inactive Co-OH and Co-O species into active CoN 4 sites. The critical transition occurs at 700 °C and becomes optimal at 900 °C, generating the highest intrinsic activity and four-electron selectivity for the oxygen reduction reaction (ORR). DFT calculations elucidate that the ORR is kinetically favored by the thermal-induced compressive strain of Co-N bonds in CoN 4 active sites formed at 900 °C. Further, we developed a two-step (i.e., Co ion doping and adsorption) Co-N-C catalyst with increased CoN 4 site density and optimized porosity for mass transport, and demonstrated its outstanding fuel cell performance and durability.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Dynamical Ion Correlations in Polymer and Membrane Electrolytes: Recent Advances and Open Questions
Ion transport in polymer and membrane electrolytes is often described using uncorrelated models like the Nernst–Einstein (NE) approximation, which link conductivity, transference number, and salt diffusivity to individual ion mobilities. However, growing evidence shows that dynamical ion correlations─arising from ion pairing, polymer-mediated coupling, confinement, and electrostatic interactions─can substantially alter macroscopic transport properties. The Onsager transport formalism offers a rigorous framework to quantify these effects via cross-correlated ionic displacements. This Perspective highlights how such correlations manifest across dry and hydrated systems, including salt-doped polymers, block copolymers, hydrogels, and ion-exchange membranes. Here, we examine key physical origins, the influence of salt chemistry and polymer structure, and open questions in measuring and controlling correlated motion. Embracing correlation-aware design enables new pathways to optimize conductivity, transference number, and selectivity─shifting the focus from individual ion mobility to engineered collective dynamics for next-generation electrolytes in energy storage and separations.
Charge transport↗
Planarized arrays of aligned, untangled multiwall carbon nanotubes with Ohmic back contacts
Vertically aligned, untangled planarized arrays of multiwall carbon nanotubes (MWNTs) with Ohmic back contacts were grown in nanopore templates on arbitrary substrates. The templates were prepared by sputter depositing Nd-doped Al films onto W-coated substrates, followed by anodization to form an aluminum oxide nanopore array. The W underlayer helps eliminate the aluminum oxide barrier that typically occurs at the nanopore bottoms by instead forming a thin WO 3 layer. The WO 3 can be selectively etched to enable electrodeposition of Co catalysts with control over the Co site density. This led to control of the site density of MWNTs grown by thermal chemical vapor deposition, with the W also serving as a back electrical contact. As a result, Ohmic contact to MWNTs was confirmed, even following ultrasonic cutting of the entire array to a uniform height.
36 MATERIALS SCIENCE↗
Phase, morphology, elemental composition, and formation mechanisms of biogenic and abiogenic Fe-Cu-sulfide nanoparticles: A comparative study on their occurrences under anoxic conditions
In this paper, we report on a systematic study on the physicochemical attributes of synthetic Fe-Cu-sulfide nanoparticles (NPs) precipitated under conditions similar to the anoxic, low temperature aqueous, sedimentary, soil and subsurface environments where these NPs have been repeatedly identified. Characterizing the basic attributes of these NPs is the first step in understanding their behaviors in various processes including in the bio-availability of essential and toxic metals, environmental remediation and resource recovery. All experiments are performed in the presence and absence of the sulfate-reducer Desulfovibrio vulgaris to elucidate biological controls on NP formation. First, the single-metal endmember NPs are determined by precipitation in solution containing either aqueous Fe(II) or Cu(II). Limited differences are observed between biogenic and abiogenic precipitates aged for up to one month; the Fe-only experiments resulted in 4-10 nm mackinawite (FeS) NPs that aggregate to form nanosheets up to ~1,000 nm in size, while the Cu-only experiments resulted in mixtures of covellite (CuS) NPs comprised of <10 nm fine nanocrystals, 20-40 x 6-9 nm nanorods and ~30 nm nanoplates. The crystal sizes of biogenic mackinawite and covellite are respectively larger and smaller than their abiogenic counterparts, indicating a mineral-specific response to biological presence. Structural defects are observable in the fine nanocrystals and nanorods of covellite in both biogenic and abiogenic experiments, indicative of intrinsic NP instability and formation mechanism via particle attachment. In contrast, covellite nanoplates are defect-free, indicating high stability and potentially rapid recrystallization following particle attachment. Next, mixed-metal sulfide NPs are precipitated at variable initial aqueous Fe-to-Cu ratios (2:1, 1:1 and 1:5). With increasing ratio of Fe-to-Cu, Fe-rich covellite, nukundamite (Cu 5.5 FeS 6.5 ), chalcopyrite (CuFeS 2 ), and Cu-rich mackinawite are formed. The Fe-rich covellite NPs are larger (100-200 nm) than covellite precipitated in the absence of Fe, indicating a role for Fe in promoting crystal growth. Chalcopyrite and nukundamite are formed through incorporation of Fe into precursor covellite NPs while retaining the original crystal morphology, as confirmed by doping a covellite suspension with aqueous Fe(II), resulting in the formation of chalcopyrite and nukundamite within days. Additionally, in the biological systems we observe the recrystallization of mackinawite to greigite (Fe 3 S 4 ) after six months of incubation in the absence of Cu, and the selective formation of chalcopyrite and nukundamite at lower initial Fe-to-Cu ratios compared to abiotic systems. These observations are consistent with NP precipitation that are influenced by the distinct (sub)micro-environments around bacterial cells compared to the bulk solution. Lastly, comparative TEM analyses indicate that the synthetic NPs are morphologically similar to NPs identified in natural environments, opening ways to studying behaviors of natural NPs using experimental approaches.
36 MATERIALS SCIENCE↗
Transition metal-doped 3C-SiC as a promising material for intermediate band solar cells
In this report the un-surveyed domain of silicon-based intermediate band solar cell (IBSC) has been studied. Intermediate band (IB) has been created in 3C-SiC through substitution of cobalt (Co) atoms within super cell structures as a consequence of interaction between the crystalline potential and spin interaction with d orbitals of Co. The band structure, density of state and absorption coefficient of the new material have been extracted. Large band gap of 3C-SiC along with the proper selection of the guest Co atoms provides both high conversion efficiency and also, the possibility to reach the theoretical optimal band gap for photovoltaic applications. However, we demonstrated that a metallic narrow IB is formed whiten the forbidden band energy of 3C-SiC when Co atoms are located inside that. The maximum conversion efficiencies near 60% and 55% are obtained under AM1.5 and AM0 spectra, respectively. Our theoretical results provide a possible way to design high efficiency solar cell based on silicon carbide.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Oxy-fluorophosphate glass doped SmO{sup 3+} as solid state dosimeter via spectroscopic techniques
In the present work, collective studies on optical, structural and magnetic properties of 0.5% SmO{sup 3+} ions in new easily melting fluorophosphate glass of the basic composition 70P{sub 2}O{sub 5}–20AlF{sub 3}–10NaF were carried out. The same combined spectral measurements (UV–Vis, FTIR, and ESR) were repeated after successive gamma irradiation. These collective spectral studies are expected to throw some insight on the effect of host fluorophosphate glass on these selected spectral properties of samarium ions together with identifying the effects of gamma irradiation on both the host fluorophosphate glass and on samarium ions and reaching to the resultant generated induced defects. The experimental results exhibit that, the slope of the UV–Vis line is sufficiently high in order to this tool is preferable to be elected as a suitable tool for the dosimetric purpose for this glass composition. The results in this manuscript propose that it is possible to use these techniques to determine if the glass sample may be used as solid-state dosimeters for gamma dose measurements in the range from 0.1 up to 15 kGy due to their linearity with the absorbed dose, color change, low fading for time periods up to 25 days and good response reproducibility.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
Unraveling Thermodynamic and Kinetic Contributions to the Stability of Doped Nanocrystalline Alloys using Nanometallic Multilayers
Abstract Targeted doping of grain boundaries is widely pursued as a pathway for combating thermal instabilities in nanocrystalline metals. However, certain dopants predicted to produce grain‐boundary‐segregated nanocrystalline configurations instead form small nanoprecipitates at elevated temperatures that act to kinetically inhibit grain growth. Here, thermodynamic modeling is implemented to select the Mo–Au system for exploring the interplay between thermodynamic and kinetic contributions to nanostructure stability. Using nanoscale multilayers and in situ transmission electron microscopy thermal aging, evolving segregation states and the corresponding phase transitions are mapped with temperature. The microstructure is shown to evolve through a transformation at lower homologous temperatures (<600 °C) where solute atoms cluster and segregate to the grain boundaries, consistent with predictions from thermodynamic models. An increase in temperature to 800 °C is accompanied by coarsening of the grain structure via grain boundary migration but with multiple pinning events uncovered between migrating segments of the grain boundary and local solute clustering. Direct comparison between the thermodynamic predictions and experimental observations of microstructure evolution thus demonstrates a transition from thermodynamically preferred to kinetically inhibited nanocrystalline stability and provides a general framework for decoupling contributions to complex stability transitions while simultaneously targeting a dominant thermal stability regime.
25 ENERGY STORAGE↗
Direct In-situ TEM Observation Of Modification Of Oxidation By The Injected Vacancies For Ni-4Al Alloy Using A Microfabricated Nanopost
Vacancy injection and selective oxidation of one specie in bimetallic alloy at high temperature is a well-known phenomenon. However, detailed understanding of the behavior of the injected vacancies and consequently their behavior and effect on oxidation remains elusive. The current research examines the oxidation of high-purity Ni doped with 4.1 at% Al using in-situ transmission electron microscopy (TEM). Experiments are performed on nanoposts fabricated from solution-annealed bulk material that are essentially single crystal samples. Initial oxidation is observed to occur by multi-site oxide nucleation, formation of an oxide shell followed by cavity nucleation and growth at the metal/oxide interface. One of the most interesting in-situ TEM observations is the formation of a cavity that leads to the faceting of the metal on (111) surface and subsequent oxidation occurring by an atomic ledge migration mechanism on the faceted metal surface. Further, it is directly observed that metal atoms diffuse through the oxide layer to combine with oxygen at the outer surface of the oxide. The present work indicates that injection of vacancies and formation of cavity will lead to a situation where the oxidation rate is essentially controlled by the low surface energy plane of the metal, rather than by the initial terminating plane at the metal surface exposed to the oxidizing environment.
36 MATERIALS SCIENCE↗
A progressive electrochemical sensor for food quality control: Reliable determination of theobromine in chocolate products using a miniaturized boron-doped diamond electrode
In the present paper, a miniaturized boron-doped diamond electrode (BDDE) is proposed as a progressive electrochemical sensor for simple, fast and reliable quantification of dimethylxanthine alkaloid, theobromine (TB). Using cyclic voltammetry, the studied xanthine provided one well-shaped, irreversible and diffusion-controlled oxidation peak at relatively high potentials (+1.2 V vs. Ag/AgCl/3 M KCl reference electrode) in the presence of 0.1 M H2SO4. After selection of suitable experimental conditions, the linear calibration curves for TB were obtained in the concentration range from 0.99 up to 54.5 μM with the sensitivity of 0.07 μA/μM providing both differential pulse (DPV) and square-wave voltammetric (SWV) techniques, respectively. The elaborated voltammetric protocol yielded low detection limits of 0.42 and 0.51 μM accompanied by adequate intra-day repeatability (relative standard deviation of 2.5 and 1.7%) using DPV and SWV procedure, respectively. The interference study revealed the reasonable selectivity when taking the target food samples into account. The practical applicability of the voltammetric protocol using a miniaturized BDDE was verified in the analysis of six commercially available brands of chocolate products with the determined mass percentages of TB ranging from 0.75 to 2.24% and from 0.69 to 2.15% using DPV and SWV procedure, respectively. The obtained results were also in a good agreement with those achieved by reference titration method with potentiometric indication. The progressive electrochemical sensor based on a miniaturized BDDE has appeared to be an attractive candidate for practical applications in food quality control. Besides, the proposed voltammetric protocol presents advantages when compared to others techniques (e.g. chromatography), concerning simplicity, cost, speed of analysis, waste generation (environmentally friendly) and samples pretreatment (only dilution in electrolyte solution prior to analysis). © 2018 Elsevier B.V.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Novel K rattling: A new route to thermoelectric materials?
We have performed ab initio molecular dynamics simulations to study the alkali-metal dynamics in the Al-doped (KAl{sub 0.33}W{sub 1.67}O{sub 6} and RbAl{sub 0.33}W{sub 1.67}O{sub 6}) and undoped (KW{sub 2}O{sub 6} and RbW{sub 2}O{sub 6}) defect pyrochlore tungstates. The K atoms exhibit novel rattling dynamics in both the doped and undoped tungstates while the Rb atoms do not. The KAl{sub 0.33}W{sub 1.67}O{sub 6} experimental thermal conductivity curve shows an unusual depression between ∼50 K and ∼250 K, coinciding with two crossovers in the K dynamics: the first at ∼50 K, from oscillatory to diffusive, and the second at ∼250 K, from diffusive back to oscillatory. We found that the low-temperature crossover is a result of the system transitioning below the activation energy of the diffusive dynamics, whereas the high-temperature crossover is driven by a complex reconstruction of the local potential around the K atoms due to the cage dynamics. This leads to a hardening of the K potential with increasing temperature. This unusual reconstruction of the potential may have important implications for the interpretation of finite-temperature dynamics based on zero-temperature potentials in similar materials. The key result is that the novel K rattling, involving local diffusion, leads to a significant reduction in the thermal conductivity. We suggest that this may open a new route in the phonon engineering of cage compounds for thermoelectric materials, where the rattlers are specifically selected to reduce the lattice thermal conductivity by the mechanism of local diffusion.
36 MATERIALS SCIENCE↗
Direct synthesis of ordered mesoporous materials from thermoplastic elastomers
Abstract The ability to manufacture ordered mesoporous materials using low-cost precursors and scalable processes is essential for unlocking their enormous potential to enable advancement in nanotechnology. While templating-based methods play a central role in the development of mesoporous materials, several limitations exist in conventional system design, including cost, volatile solvent consumption, and attainable pore sizes from commercial templating agents. This work pioneers a new manufacturing platform for producing ordered mesoporous materials through direct pyrolysis of crosslinked thermoplastic elastomer-based block copolymers. Specifically, olefinic majority phases are selectively crosslinked through sulfonation reactions and subsequently converted to carbon, while the minority block can be decomposed to form ordered mesopores. We demonstrate that this process can be extended to different polymer precursors for synthesizing mesoporous polymer, carbon, and silica. Furthermore, the obtained carbons possess large mesopores, sulfur-doped carbon framework, with tailorable pore textures upon varying the precursor identities.
36 MATERIALS SCIENCE↗