Experimental Characterization Techniques Research Articles

Exogenous Protein Delivery of Ionic Liquid-Mediated HMGB1 Coating on Titanium Implants.

Strategies for modifying titanium (Ti) implant surfaces are becoming increasingly popular to enhance osseointegration during acute and inflammatory healing stages. In this study, two dicationic imidazolium-based ionic liquids (IonLs) containing phenylalanine and methionine anions (IonL-Phe(1,10-bis(3-methylimidazolium-1-yl)decane diphenylalanine) and IonL-Met(1,10-bis(3-methylimidazolium-1-yl)decane dimethionine)) were investigated to stably deliver exogenous proteins on Ti to promote osseointegration. The protein selected for this study is High-Mobility Group Box 1 (HMGB1), which recruits inflammatory and mesenchymal stem cells to the implantation site, contributing to healing. To explore IonL-Ti interactions and HMGB1 stability on the IonL-coated surface, experimental characterization techniques including X-ray photoelectron spectroscopy, scanning electron microscopy, dynamic scanning calorimetry (DSC), and liquid chromatography mass spectrometry (LC-MS) were used along with molecular dynamics (MD) computer simulations to provide a detailed molecular level description. Results show well-structured IonL molecules on the Ti surface that impact protein crystallization and coating morphology. IonL cations and anions were found to bind strongly to oppositely charged residues of the protein. LC-MS/MS reveals that HMGB1 B-box lysine residues bind strongly to the IonLs. Stronger interactions of HMGB1 with Ion-Phe in contrast to IonL-Met results in greater retention capacity of HMGB1 in the IonL-Phe coating. Overall, this study provides evidence that the selected IonLs strongly interact with HMGB1, which can be a potential surface treatment for bone-implantable Ti devices.

Ni/Fe Bimetallic Ions Co-Doped Manganese Dioxide Cathode Materials for Aqueous Zinc-Ion Batteries

The slow diffusion dynamics hinder aqueous MnO2/Zn batteries’ further development. Here, a Ni/Fe bimetallic co-doped MnO2 (NFMO) cathode material was studied by density functional theory (DFT) calculation and experimental characterization techniques, such as cyclic voltammetry (CV), galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectra (EIS). The results indicated that the energy band structure and electronic state of MnO2 were effectively optimized due to the simultaneous incorporation of strongly electronegative Ni and Fe ions. Consequently, the NFMO cathode material exhibited a faster charge transfer and ion diffusion dynamics than MnO2 (MO), thus, the assembled NFMO/Zn batteries delivered excellent rate performance (181 mA h g−1 at 3 A g−1). The bimetallic ions co-doping strategy provides new directions for the development of oxide cathode materials towards high-performance aqueous zinc-ion batteries.

Development of a Background-Oriented Schlieren (BOS) System for Thermal Characterization of Flow Induced by Plasma Actuators

Cold climate regions have great potential for wind power generation. The available wind energy in these regions is about 10% higher than in other regions due to higher wind speeds and increased air density. However, these regions usually have favorable icing conditions that lead to ice accumulation on the wind turbine blades, which in turn increases the weight of the blades and disrupts local airflow, resulting in a reduction in wind turbine performance. Considering this problem, plasma actuators have been proposed as devices for simultaneous flow control and deicing. These devices transfer momentum to the local airflow, improving the aerodynamic performances of the turbine blades while producing significant thermal effects that can be used to prevent ice formation. Considering the potential application of plasma actuators for simultaneous flow control and deicing, it is very important to investigate the thermal effects induced by these devices. However, due to the significant electromagnetic interference generated by the operation of these devices, there is a lack of experimental techniques that can be used to analyze them. In the current work, a background-oriented Schlieren system was developed and is presented as a new experimental technique for the thermal characterization of the plasma-induced flow. For the first time, the induced flow temperatures are characterized for plasma actuators with different dielectric materials and different dielectric thicknesses. The results demonstrate that, due to the plasma discharge, the temperature of the plasma-induced flow increases with the increase of the applied voltage and may achieve temperatures five times higher than the room temperature, which proves the potential of plasma actuators for deicing applications. The results are presented and discussed with respect to the potential application of plasma actuators for simultaneous flow control and deicing of wind turbine blades.

Smartphone-based particle image velocimetry for cardiovascular flows applications: A focus on coronary arteries.

An experimental set-up is presented for the in vitro characterization of the fluid dynamics in personalized phantoms of healthy and stenosed coronary arteries. The proposed set-up was fine-tuned with the aim of obtaining a compact, flexible, low-cost test-bench for biomedical applications. Technically, velocity vector fields were measured adopting a so-called smart-PIV approach, consisting of a smartphone camera and a low-power continuous laser (30mW). Experiments were conducted in realistic healthy and stenosed 3D-printed phantoms of left anterior descending coronary artery reconstructed from angiographic images. Time resolved image acquisition was made possible by the combination of the image acquisition frame rate of last generation commercial smartphones and the flow regimes characterizing coronary hemodynamics (velocities in the order of 10cm/s). Different flow regimes (Reynolds numbers ranging from 20 to 200) were analyzed. The smart-PIV approach was able to provide both qualitative flow visualizations and quantitative results. A comparison between smart-PIV and conventional PIV (i.e., the gold-standard experimental technique for bioflows characterization) measurements showed a good agreement in the measured velocity vector fields for both the healthy and the stenosed coronary phantoms. Displacement errors and uncertainties, estimated by applying the particle disparity method, confirmed the soundness of the proposed smart-PIV approach, as their values fell within the same range for both smart and conventional PIV measured data (≈5% for the normalized estimated displacement error and below 1.2 pixels for displacement uncertainty). In conclusion, smart-PIV represents an easy-to-implement, low-cost methodology for obtaining an adequately robust experimental characterization of cardiovascular flows. The proposed approach, to be intended as a proof of concept, candidates to become an easy-to-handle test bench suitable for use also outside of research labs, e.g., for educational or industrial purposes, or as first-line investigation to direct and guide subsequent conventional PIV measurements.

Advanced in-situ experimental techniques for characterization of deformation mechanisms in magnesium alloys

A combination of advanced in-situ experimental techniques, comprised of neutron diffraction, acoustic emission (AE), and in-situ electron backscattered diffraction (EBSD) was selected to provide extensive insight into the deformation behavior of magnesium alloys based on their mutual complementarity. The potential and limitations of these techniques were shown and discussed in the scope of the study of the influence of the crystallographic texture influence on the activity of individual deformation mechanisms in a hot-rolled sheet of the AZ31 magnesium alloy. The neutron diffraction experiments coupled with a recording of the AE signal allowed monitoring of the twinning activity and the evolution of its dynamics from nucleation toward twin growth. The AE suggested microplastic behavior, which was confirmed by the lattice strain evolution analysis for the sample compressed in the sheet normal direction. The in-situ EBSD experiments provided direct observation of the deformed microstructure, including the formation of twinning bands and the transition from twin nucleation to growth with progressing strain, being in very good agreement with the indirect neutron diffraction and AE measurements. Furthermore, the subsequent analysis of the EBSD maps enabled the quantification of the twinned volume fraction and its qualitative comparison with the evolution measured by neutron diffraction. The EBSD-based slip trace analysis revealed a notable non-Schmid basal activity and offered insight into the mechanisms accommodating strain once the twinning was exhausted.

Molecular evolution mechanism of flow-induced crystallization in polyphenylene sulfide

Microstructures play a significant role on the mechanical performance of materials. Based on the experimental characterization and molecular modeling techniques, this work assessed the influences on the mechanical properties of semi-crystalline 1-4 polyphenylene sulfide (PPS) from pressure and temperature. It was found that the shear deformation in the flow field is a key factor that induces the transformation from amorphous polymers to precursors. Though, pressure can accelerate the transition of precursors to crystals, proportion of precursors in the PPS is not observed under higher pressure. The understanding established in this work is helpful to identify optimal processing parameters during the manufacturing of PPS for target applications.

(Invited) Computational Modeling of Photoelectrochemical Processes for Hydrogen Production

Recent progresses in predictive modeling methods together with high-fidelity experimental characterization techniques that take device operation condition into consideration led to significant advancements in understanding how microscopic interfacial processes propagate to macroscopic device behavior. In this talk, we will overview our computational modeling efforts within HydroGEN consortium based on various method such as ab-initio atomistic modeling and continuum model, wherein the state-of-art characterization techniques are fully leveraged for the reliability of our interpretation. As examples, we will present our recent activities to improve understanding about the mechanisms that dictate performance and durability of hydrogen production devices, where considering operating conditions and integration with experimental characterization often played critical roles [1-6]. More specifically, we will discuss how computational models have helped to elucidate mechanisms of interface chemistry, formation of new phases, and the impact of interfaces on key reaction pathways that are intimately related to the device performance and durability, wherein experimental characterization data was used as the constraint for our models and obtain new understanding of interfacial phenomena relevant for the performance of hydrogen production techniques. Finally, we will discuss how the obtained knowledge can be used to develop strategies for improving materials used in hydrogen production technologies. This work was supported by the U.S. Department of Energy, Energy Efficiencies and Renewable Energies Office, Hydrogen and Fuel Cells Technologies Office, and was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under contract DE-AC52-07NA27344.

LigninGraphs: lignin structure determination with multiscale graph modeling

Lignin is an aromatic biopolymer found in ubiquitous sources of woody biomass. Designing and optimizing lignin valorization processes requires a fundamental understanding of lignin structures. Experimental characterization techniques, such as 2D-heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) spectra, could elucidate the global properties of the polymer molecules. Computer models could extend the resolution of experiments by representing structures at the molecular and atomistic scales. We introduce a graph-based multiscale modeling framework for lignin structure generation and visualization. The framework employs accelerated rejection-free polymerization and hierarchical Metropolis Monte Carlo optimization algorithms. We obtain structure libraries for various lignin feedstocks based on literature and new experimental NMR data for poplar wood, pinewood, and herbaceous lignin. The framework could guide researchers towards feasible lignin structures, efficient space exploration, and future kinetics modeling. Its software implementation in Python, LigninGraphs, is open-source and available on GitHub.Graphical abstract

Facile preparation of anti-biofouling reverse osmosis membrane embedded with polydopamine-nano copper functionality: Performance and mechanism

In this study, we conducted a facile membrane modification process by mild electroless deposition of copper nanoparticles (CuNPs) integrating polydopamine (PDA) coating to combat biofouling of thin-film composite (TFC) reverse osmosis (RO) membranes. Various experimental tests and characterization techniques have been applied to reveal the anti-biofouling performance and underlying mechanism of prepared membranes (i.e., Cu/PDA/TFC membrane). The successful functionalization with PDA and CuNPs highly enhanced the anti-fouling properties of Cu/PDA/TFC membrane, as evidenced by 45%, 40% and 37% respectively lower adsorption of bovine serum albumin, humic acid, and lipopolysaccharide in static adhesion assays. A significant decreased membrane-foulant adhesion forces by 63% was observed for Cu/PDA/TFC membrane compared to control membrane, which is ascribed to enhanced membrane surface hydrophilicity after PDA coating. Moreover, The Cu/PDA/TFC membranes presented significantly decreased cell viability (E. coli from 90% to 22%, P. aeruginosa from 89% to 26%, and S. aureus from 84% to 18%), and reduced adenosine tri-phosphate (ATP) content after 3 h bacterial exposure (E. coli by 57%, P. aeruginosa by 50%, and S. aureus by 56%). Assessment on cell viability and metabolic activities of bacteria deposited on membrane indicate that contact-mediated toxicity contributed to the antibacterial mechanism of Cu/PDA//TFC membrane. In addition, the reduced viability of the planktonic cells at the membrane surroundings under durable copper leaching (∼17 mg/m2 to ∼9 mg/m2) suggest that release of antibacterial Cu2+ ions also played an important role in membrane antibacterial mechanism. Both contact-mediated and Cu2+ release-based antibacterial mechanisms endow Cu/PDA/TFC membrane with excellent anti-biofouling capacity under long-term dynamic condition, with 45% lower flux decline compared to the control membrane.

Construction of multistage porous carbon materials for the hydrochlorination of acetylene: Impact of nitrogen incorporation

The benchmark carbon-based catalyst, activated carbon (AC), has a low catalytic activity due to its uniform surface charge distribution and stable structure. To overcome these problems, melamine-phenol-formaldehyde (MPF) resin, which is rich in pyridinic N and pyrrolic N, multi-porous C-N materials rich with defect sites were synthesized in situ by heat treatment using silica sol as the template and phenol, melamine, and formaldehyde as the carbon and nitrogen sources. The experimental results and characterization techniques revealed that carbon materials with abundant hierarchical pores and local C-N active sites were constructed by incorporating heteroatom-containing groups. Hydrogen chloride and acetylene molecules were activated due to the high electronegativity of defective sites, and the synergistic interactions between pyridinic N and π-containing functional groups (C=C, triazine ring, etc.). The structure-performance relationship was also clarified using DFT calculations. In addition, the strong interactions between heteroatomic sites and metal species also made MPF-800 an admirable metal catalyst support. Overall, the disadvantages of acetylene hydrochlorination catalyzed by benchmark AC were resolved.

Principles of Cation-π Interactions for Engineering Mussel-Inspired Functional Materials.

Supramolecular assembly is commonly driven by noncovalent interactions (e.g., hydrogen bonding, electrostatic, hydrophobic, and aromatic interactions) and plays a predominant role in multidisciplinary research areas ranging from materials design to molecular biology. Understanding these noncovalent interactions at the molecular level is important for studying and designing supramolecular assemblies in chemical and biological systems. Cation-π interactions, initially found through their influence on protein structure, are generally formed between electron-rich π systems and cations (mainly alkali, alkaline-earth metals, and ammonium). Cation-π interactions play an essential role in many biological systems and processes, such as potassium channels, nicotinic acetylcholine receptors, biomolecular recognition and assembly, and the stabilization and function of biomacromolecular structures. Early fundamental studies on cation-π interactions primarily focused on computational calculations, protein crystal structures, and gas- and solid-phase experiments. With the more recent development of spectroscopic and nanomechanical techniques, cation-π interactions can be characterized directly in aqueous media, offering opportunities for the rational manipulation and incorporation of cation-π interactions into the design of supramolecular assemblies. In 2012, we reported the essential role of cation-π interactions in the strong underwater adhesion of Asian green mussel foot proteins deficient in l-3,4-dihydroxyphenylalanine (DOPA) via direct molecular force measurements. In another study in 2013, we reported the experimental quantification and nanomechanics of cation-π interactions of various cations and π electron systems in aqueous solutions using a surface forces apparatus (SFA).Over the past decade, much progress has been achieved in probing cation-π interactions in aqueous solutions, their impact on the underwater adhesion and cohesion of different soft materials, and the fabrication of functional materials driven by cation-π interactions, including surface coatings, complex coacervates, and hydrogels. These studies have demonstrated cation-π interactions as an important driving force for engineering functional materials. Nevertheless, compared to other noncovalent interactions, cation-π interactions are relatively less investigated and underappreciated in governing the structure and function of supramolecular assemblies. Therefore, it is imperative to provide a detailed overview of recent advances in understanding of cation-π interactions for supramolecular assembly, and how these interactions can be used to direct supramolecular assembly for various applications (e.g., underwater adhesion). In this Account, we present very recent advances in probing and applying cation-π interactions for mussel-inspired supramolecular assemblies as well as their structural and functional characteristics. Particular attention is paid to experimental characterization techniques for quantifying cation-π interactions in aqueous solutions. Moreover, the parameters responsible for modulating the strengths of cation-π interactions are discussed. This Account provides useful insights into the design and engineering of smart materials based on cation-π interactions.

Experimental characterization techniques for plasmon-assisted chemistry.

Plasmon-assisted chemistry is the result of a complex interplay between electromagnetic near fields, heat and charge transfer on the nanoscale. The disentanglement of their roles is non-trivial. Therefore, a thorough knowledge of the chemical, structural and spectral properties of the plasmonic/molecular system being used is required. Specific techniques are needed to fully characterize optical near fields, temperature and hot carriers with spatial, energetic and/or temporal resolution. The timescales for all relevant physical and chemical processes can range from a few femtoseconds to milliseconds, which necessitates the use of time-resolved techniques for monitoring the underlying dynamics. In this Review, we focus on experimental techniques to tackle these challenges. We further outline the difficulties when going from the ensemble level to single-particle measurements. Finally, a thorough understanding of plasmon-assisted chemistry also requires a substantial joint experimental and theoretical effort.

Experimental Characterization Techniques for Solid-Liquid Slurry Flows in Pipelines: A Review

In industrial environments, having instrumentation able to attain fast, accurate, and autonomous measurements is pivotal to understanding the dynamics of liquid and particles during transport. Ideally, these instruments, consisting of either probes or sensors, should be robust, fast, and unintrusive, i.e., not cause interference on the very flows being monitored, and require minimal maintenance. Beyond monitoring, the process knowledge gained through real time inspection allows teams to make informed technical decisions based on particle behavior, i.e., settling of particles causing pipe wear and clustering or blockages that can damage the unit or cause shutdowns, both of which with economical drawbacks. The purpose of this review is to examine experimental measurement techniques used to characterize physical properties and operational parameters of solid-liquid slurry flows, focusing on non-ionizing radiation methods. With this text the intent is not to provide an exhaustive examination of each individual technique but rather an overview on the most pertinent types of instrumentation, which will be presented, in addition to application examples from the literature, while directing the reader for pertinent seminal and review papers for a more in-depth analysis.

Developing a solid decomposition kinetics extraction framework for detailed chemistry pyrolysis and combustion modelling of building polymer composites

Combustibility of insulation and external façade remains a critical issue for many countries as they are commonly found in modern building structures. While standardised fire tests can be carried out to examine the flammability limits of building polymers, they cannot inform us of the toxicity and smoke productions of the underlying materials. With recent advancements in computational approaches (i.e. surface regression porous media pyrolysis model as depicted in Fig. 1) and its synergy with experimental characterisation techniques, a systematic framework is proposed to robustly realise the potential risks associated with any building polymer samples. This involves a five-step procedure including (i) performing TGA on the core polymer materials to acquire thermal and gas decomposition data; (ii) extracting pyrolysis kinetics data from TGA results via an initial estimation of the Kissinger–Akahira–Sunose method; (iii) optimise kinetics parameters via a shuffled complex evolution (SCE) algorithms to match DTG curves for an accurate representation of the degradation behaviour; (iv) conduct reduce-scale simulations via computational fluid dynamics (CFD) in a cone calorimeter environment and compare against experimental data with/without aluminium covering for validation; (v) use the validated model to predict gaseous products, toxicity and soot particles releases and benchmark against Cone Calorimeter data. Once this database is established, it can be used for up-scaled modelling in a multiple-storey building setting. In this work, one of the most commonly applied building polymers for insulation applications and external façade systems: polyethelene (PE) is taken as an example to establish a numerical database. To learn whether the effect of flame-retardants that suppresses the flammability and intermediate combustion gases releases of PE can be replicated in the CFD modelling, the PE was also treated by plasma treatment subsequently immersed by graphene oxide as fillers. The reductions in heat, smoke and carbon monoxide releases were benchmarked against the pure PE data while the increased char formation offered by the carbon-based enhancing agent is examined from a numerical perspective.

Soft-Tissue Material Properties and Mechanogenetics during Cardiovascular Development.

During embryonic development, changes in the cardiovascular microstructure and material properties are essential for an integrated biomechanical understanding. This knowledge also enables realistic predictive computational tools, specifically targeting the formation of congenital heart defects. Material characterization of cardiovascular embryonic tissue at consequent embryonic stages is critical to understand growth, remodeling, and hemodynamic functions. Two biomechanical loading modes, which are wall shear stress and blood pressure, are associated with distinct molecular pathways and govern vascular morphology through microstructural remodeling. Dynamic embryonic tissues have complex signaling networks integrated with mechanical factors such as stress, strain, and stiffness. While the multiscale interplay between the mechanical loading modes and microstructural changes has been studied in animal models, mechanical characterization of early embryonic cardiovascular tissue is challenging due to the miniature sample sizes and active/passive vascular components. Accordingly, this comparative review focuses on the embryonic material characterization of developing cardiovascular systems and attempts to classify it for different species and embryonic timepoints. Key cardiovascular components including the great vessels, ventricles, heart valves, and the umbilical cord arteries are covered. A state-of-the-art review of experimental techniques for embryonic material characterization is provided along with the two novel methods developed to measure the residual and von Mises stress distributions in avian embryonic vessels noninvasively, for the first time in the literature. As attempted in this review, the compilation of embryonic mechanical properties will also contribute to our understanding of the mature cardiovascular system and possibly lead to new microstructural and genetic interventions to correct abnormal development.

Large-Scale Synthesis of Metal Additively-Manufactured Microstructures Using Markov Random Fields

A data-driven framework is developed and examined for creating spatially-varying crystallographic textures over component-scale Computer-Aided Design (CAD) models. Here, a set of three orthogonal 2D micrographs of an Additively-Manufactured (AM) specimen are first obtained experimentally through Electron Backscatter Diffraction (EBSD) and subsequently converted to a 3D representative unit cell using the Markov Random Field (MRF) technique. Features such as grain size, crystallographic orientation, and grain boundary misorientation distributions are used to validate the reconstructed 3D microstructure against input experimental EBSD images. The variations of microstructural features during a powder-based additive manufacturing process are subsequently modeled by merging patches from the 3D snapshot of AM microstructural unit cell in a part-scale geometry using a tensor-based optimization process. The optimization algorithm repeatedly pastes microstructural elements from the reconstructed MRF unit cell onto the geometrical CAD domain until it is entirely covered. Here, through a simple Graphical User Interface (GUI), the user specifies a tensor field over the volumetric CAD model, defining the local control over grain-scale, anisotropy, and crystal growth orientation. This new approach provides a workflow for reconstructing global maps of AM microstructures in real-time by embedding site-specific images based on known AM microstructural patterns seen in experimental characterization techniques. The numerical results are helpful specifically for the visualization of process–microstructure relationships in metal additive manufacturing techniques.

Porous liquids - the future is looking emptier.

The development of microporosity in the liquid state is leading to an inherent change in the way we approach applications of functional porosity, potentially allowing access to new processes by exploiting the fluidity of these new materials. By engineering permanent porosity into a liquid, over the transient intermolecular porosity in all liquids, it is possible to design and form a porous liquid. Since the concept was proposed in 2007, and the first examples realised in 2015, the field has seen rapid advances among the types and numbers of porous liquids developed, our understanding of the structure and properties, as well as improvements in gas uptake and molecular separations. However, despite these recent advances, the field is still young, and with only a few applications reported to date, the potential that porous liquids have to transform the field of microporous materials remains largely untapped. In this review, we will explore the theory and conception of porous liquids and cover major advances in the area, key experimental characterisation techniques and computational approaches that have been employed to understand these systems, and summarise the investigated applications of porous liquids that have been presented to date. We also outline an emerging discovery workflow with recommendations for the characterisation required at each stage to both confirm permanent porosity and fully understand the physical properties of the porous liquid.

A combined experimental and molecular simulation study on stress generation phenomena during the Ziegler-Natta polyethylene catalyst fragmentation process.

The morphology of particles obtained under different pre-polymerization conditions has been connected to the stress generation mechanism at the polymer/catalyst interface. A combination of experimental characterization techniques and atomistic molecular dynamics simulations allowed a systematic investigation of experimental conditions leading to a certain particle morphology, and hence to a final polymer with specific features. Atomistic models of nascent polymer phases in contact with magnesium dichloride surfaces have been developed and validated. Using these detailed models, in the framework of McKenna's hypothesis, the pressure increase due to the polymerization reaction has been calculated under different conditions and is in good agreement with experimental scenarios. This molecular scale knowledge and the proposed investigation strategy would allow the pre-polymerization conditions to be better defined and the properties of the nascent polymer to be tuned, ensuring proper operability along the whole polymer production process.

Ceria-supported niobium oxide catalyst for low-temperature oxidation of 1,3-butadiene

Low-temperature oxidation represents an economically efficient way to convert spinoff hydrocarbons such as butadiene into nontoxic species. This study investigates the catalytic oxidation of 1,3-butadiene over ceria-supported niobium oxide, exploring the synthesis routes and catalytic performances. Experimental characterization techniques, including X-ray spectroscopy and diffractometry, microscopy, and other micro-characterisations, elucidate the structure of the catalysts as corroborated by the density functional theory (DFT) method. DFT calculations constructed the underlying oxidative reaction mechanisms that ensue through accessible activation energies in steps that feature subsequent CC bond fissions, H transfer reactions, CO desorption, and formation of CO2 molecules. The results show that, the niobium oxide assumes mainly the form of Nb2O5 on ceria supports, and plays a significant role in switching the physicochemical nature of ceria and the resulting catalysts. Despite a relatively lower surface area, the NbOx/CeO2 catalysts exhibit superior performances in the conversion of butadiene compared to pure ceria. The catalyst prepared with 10 wt.% of Nb has the best catalytic performance with 82% conversion of butadiene, highest reaction rate, and selectivity towards CO2 of 95% at the temperature range of 300 – 400 °C and a gas hourly space velocity (GHSV) of 34,600 h−1. Obtained results entail practical environmental implications in the catalytic destruction of stable hydrocarbon species.

Atomically Dispersed Heteronuclear Dual-Atom Catalysts: A New Rising Star in Atomic Catalysis.

Atomic catalysts (AC) are gaining extensive research interest as the most active new frontier in heterogeneous catalysis due to their unique electronic structures and maximum atom-utilization efficiencies. Among all the atom catalysts, atomically dispersed heteronuclear dual-atom catalysts (HDACs), which are featured with asymmetric active sites, have recently opened new pathways in the field of advancing atomic catalysis. In this review, the up-to-date investigations on heteronuclear dual-atom catalysts together with the last advances on their theoretical predictions and experimental constructions are summarized. Furthermore, the current experimental synthetic strategies and accessible characterization techniques for these kinds of atomic catalysts, are also discussed. Finally, the crucial challenges in both theoretical and experimental aspects, as well as the future prospects of HDACs for energy-related applications are provided. It is believed that this review will inspire the rational design and synthesis of the new generation of highly effective HDACs.