In situ Dispersed Nano-Au on Zr-Suboxides as Active Cathode for Direct CO2 Electroreduction in Solid Oxide Electrolysis Cells.

CO2 electrochemical reduction in solid oxide electrolysis cells is an effective way to combine CO2 conversion and renewable electricity storage. A Au layer is often used as a current collector, whereas Au nanoparticles are rarely used as a cathode because it is difficult to keep nanosized Au at high temperatures. Here we dispersed a Au layer into Au nanoparticles (down to 2 nm) at 800 °C by applying high voltages. A 75-fold decrease in the polarization resistance was observed, accompanied by a 38-fold improvement in the cell current density. Combining electronic microscopy, in situ near-ambient pressure X-ray photoelectron spectroscopy, and theoretical calculations, we found that the interface between the Au layer and the electrolyte (yttria-stabilized zirconia (YSZ)) was reconstructed into nano-Au/Zr-suboxide interfaces, which are active sites that show a much lower reaction activation energy than that of the Au/YSZ interface. The formation of Zr-suboxides promotes Au dispersion and Au nanoparticle stabilization due to the strong interaction between Au and Zr-suboxides.

An Integrated Fuzzy C-Means Method for Missing Data Imputation Using Taxi GPS Data.

Various traffic-sensing technologies have been employed to facilitate traffic control. Due to certain factors, e.g., malfunctioning devices and artificial mistakes, missing values typically occur in the Intelligent Transportation System (ITS) sensing datasets, resulting in a decrease in the data quality. In this study, an integrated imputation algorithm based on fuzzy C-means (FCM) and the genetic algorithm (GA) is proposed to improve the accuracy of the estimated values. The GA is applied to optimize the parameter of the membership degree and the number of cluster centroids in the FCM model. An experimental test of the taxi global positioning system (GPS) data in Manhattan, New York City, is employed to demonstrate the effectiveness of the integrated imputation approach. Three evaluation criteria, the root mean squared error (RMSE), correlation coefficient (R), and relative accuracy (RA), are used to verify the experimental results. Under the ±5% and ±10% thresholds, the average RAs obtained by the integrated imputation method are 0.576 and 0.785, which remain the highest among different methods, indicating that the integrated imputation method outperforms the history imputation method and the conventional FCM method. On the other hand, the clustering imputation performance with the Euclidean distance is better than that with the Manhattan distance. Thus, our proposed integrated imputation method can be employed to estimate the missing values in the daily traffic management.

Electrochemical Cutting in Weak Aqueous Electrolytes: The Strategy for Efficient and Controllable Preparation of Graphene Quantum Dots.

The controllable and efficient electrochemical preparation of highly crystalline graphene quantum dots (GQDs) in an aqueous system is still challenging. Here, we developed a weak electrolyte-based (typically an ammonia solution) electrochemical method to enhance the oxidation and cutting process and therefore achieve a high yield of GQDs. The yield of GQDs (3-8 nm) is 28%, approximately 28 times higher than the yield of GQDs prepared by other strong electrolytes. The whole preparation process can be accomplished within 2 h because of the effective free radical oxidation process and the suppressed intercalation-induced exfoliation in weakly ionized aqueous electrolytes. The GQDs also showed excellent crystallinity which is obviously better than the crystallinity of GQDs obtained via bottom-up approaches. Moreover, amino-functionalization of GQDs can be realized by manipulating the electrolyte concentration. We further demonstrate that the proposed method can also be expanded to other weak electrolytes (such as HF and H2S) and different anode precursor materials (such as graphene/graphite papers, carbon fibers, and carbon nanotubes).

Encapsulated Silver Nanoparticles Can Be Directly Converted to Silver Nanoshell in the Gas Phase.

We report, for the first time, that an encapsulated silver nanoparticle can be directly converted to a silver nanoshell through a nanoscale localized oxidation and reduction process in the gas phase. Silver can be etched when exposed to a mixture of NH3/O2 gases through a mechanism analogous to the formation of aqueous Tollens' reagent, in which a soluble silver-ammonia complex was formed. Starting with Ag@resorcinol-formaldehyde (RF) resin core-shell nanoparticles, we demonstrate that RF-core@Ag-shell nanoparticles can be prepared successfully when the etching rate and RF thickness were well controlled. Due to the strong surface plasmon resonance (SPR) coupling effect among neighboring silver nanoparticles, the RF@Ag nanoparticle showed great SPR and SERS performance. This process provides a general route to the conversion of Ag-core to Ag-shell nanostructures and might be extended to other systems.

CO2 activation and carbonate intermediates: an operando AP-XPS study of CO2 electrolysis reactions on solid oxide electrochemical cells.

Through the use of ambient pressure X-ray photoelectron spectroscopy and specially designed ceria-based solid oxide electrochemical cells, carbon dioxide (CO2) electrolysis reactions (CO2 + 2e(-)→ CO + O(2-)) and carbon monoxide (CO) electro-oxidation reactions (CO + O(2-)→ CO2 + 2e(-)) over cerium oxide electrodes have been investigated in the presence of 0.5 Torr CO-CO2 gas mixtures at ∼600 °C. Carbonate species (CO3(2-)) are identified on the ceria surface as reaction intermediates. When CO2 electrolysis is promoted on ceria electrodes at +2.0 V applied bias, we observe a higher concentration of CO3(2-) over a 400 µm-wide active region on the ceria surface, accompanied by Ce(3+)/Ce(4+) redox changes. This increase in the CO3(2-) steady-state concentration suggests that the process of pre-coordination of CO2 to the ceria surface to form a CO3(2-) intermediate (CO2(g) + O(2-)(surface)→ CO3(2-)(surface)) precedes a rate-limiting electron transfer process involving CO3(2-) reduction to give CO and oxide ions (CO3(2-)(surface) + 2Ce(3+)→ CO(g) + 2O(2-)(surface) + 2Ce(4+)). When the applied bias is switched to -1.5 V to promote CO electro-oxidation on ceria, the surface CO3(2-) concentration slightly decreases from the equilibrium value, suggesting that the electron transfer process is also a rate-limiting process in the reverse direction.

A near ambient pressure XPS study of subnanometer silver clusters on Al2O3 and TiO2 ultrathin film supports.

We have investigated model systems of silver clusters with different sizes (3 and 15 atoms) deposited on alumina and titania supports using ambient pressure X-ray photoelectron spectroscopy. The electronic structures of silver clusters and support materials are studied upon exposure to various atmospheres (ultrahigh vacuum, O2 and CO) at different temperatures. Compared to bulk silver, the binding energies of silver clusters are about 0.55 eV higher on TiO2 and 0.95 eV higher on Al2O3 due to the final state effect and the interaction with supports. No clear size effect of the silver XPS peak is observed on different silver clusters among these samples. Silver clusters on titania show better stability against sintering. Al 2p and Ti 2p core level peak positions of the alumina and titania support surfaces change upon exposure to oxygen while the Ag 3d core level position remains unchanged. We discuss the origin of these core level shifts and their implications for catalytic properties of Ag clusters.

Direct work function measurement by gas phase photoelectron spectroscopy and its application on PbS nanoparticles.

Work function is a fundamental property of a material's surface. It is playing an ever more important role in engineering new energy materials and efficient energy devices, especially in the field of photovoltaic devices, catalysis, semiconductor heterojunctions, nanotechnology, and electrochemistry. Using ambient pressure X-ray photoelectron spectroscopy (APXPS), we have measured the binding energies of core level photoelectrons of Ar gas in the vicinity of several reference materials with known work functions (Au(111), Pt(111), graphite) and PbS nanoparticles. We demonstrate an unambiguously negative correlation between the work functions of reference samples and the binding energies of Ar 2p core level photoelectrons detected from the Ar gas near the sample surface region. Using this experimentally determined linear relationship between the surface work function and Ar gas core level photoelectron binding energy, we can measure the surface work function of different materials under different gas environments. To demonstrate the potential applications of this ambient pressure XPS technique in nanotechnology and solar energy research, we investigate the work functions of PbS nanoparticles with various capping ligands: methoxide, mercaptopropionic acid, and ethanedithiol. Significant Fermi level position changes are observed for PbS nanoparticles when the nanoparticle size and capping ligands are varied. The corresponding changes in the valence band maximum illustrate that an efficient quantum dot solar cell design has to take into account the electrochemical effect of the capping ligand as well.

Oxidation and reduction of size-selected subnanometer Pd clusters on Al2O3 surface.

In this paper, we investigate uniformly dispersed size-selected Pd(n) clusters (n = 4, 10, and 17) on alumina supports. We study the changes of clustered Pd atoms under oxidizing and reducing (O2 and CO, respectively) conditions in situ using ambient pressure XPS. The behavior of Pd in the clusters is quite different from that of Pd foil under the same conditions. For all Pd clusters, we observe only one Pd peak. The binding energy of this Pd 3d peak is ~1-1.4 eV higher than that of metallic Pd species and changes slightly in CO and O2 environments. On the Pd foil however many different Pd species co-exist on the surface and change their oxidation states under different conditions. We find that the Pd atoms in direct contact with Al2O3 differ in oxidation state from the surface Pd atoms in a foil under reaction conditions. Compared to previous literature, we find that Pd 3d peak positions are greatly influenced by the different types of Al2O3 supports due to the combination of both initial and final state effects.

Impact of vehicle type, tyre feature and driving behaviour on tyre wear under real-world driving conditions.

Tyre wear generates not only large pieces of microplastics but also airborne particle emissions, which have attracted considerable attention due to their adverse impacts on the environment, human health, and the water system. However, the study on tyre wear is scarce in real-world driving conditions. In the present study, the left-front and left-rear tyre wear in terms of volume lost in mm3 of 76 taxi cars was measured about every three months. This study covered 22 months from September 2019 to June 2021 and included more than 500 measurements in total. Some of the data was used to evaluate the effects of vehicle type and tyre type on tyre wear. In addition, a machine learning method (i.e., Extreme gradient boosting (XGBoost)) was used to probe the effect of driving behaviour on tyre wear by monitoring real-time driving behaviour. The current statistical results showed that, on average, the tyre wear was 72 mg veh-1 km-1 for a hybrid car and 53 mg veh-1 km-1 for a conventional internal combustion engine car. The average tyre wear measured for a taxi vehicle configuration featuring winter tyres was 160 mg veh-1 km-1, which was 1.4 and 3.0 times as much as those with all-season tyres and summer tyres, respectively. The wear rate of left-front tyres was 1.7 times higher than that of left-rear tyres. The XGBoost results indicated that compared to driving behaviour, tyre type and tyre position had more important effects on tyre wear. Among driving behaviours, braking and accelerating events presented the most considerable impact on tyre wear, followed by cornering manoeuvres and driving speed. Thus, it seems that limiting harsh braking and acceleration has the potential to reduce tyre wear significantly.

Ambient pressure mapping of resonant Auger spectroscopy at BL02B01 at the Shanghai Synchrotron Radiation Facility.

During the past few decades, resonant Auger spectroscopy (RAS) has presented some advantages in elucidating the electronic structure of free molecules, liquids, and solids. To further extend the application of RAS in complex in situ environments, the ambient pressure system should be developed to characterize the gas-solid and liquid-solid interfaces. In this paper, we describe the design and performance of an ambient pressure mapping of resonant Auger spectroscopy (mRAS) system newly developed at BL02B01 at the Shanghai Synchrotron Radiation Facility. This system is unique in that the ambient pressure soft x-ray absorption spectroscopy (sXAS) can be measured in Auger electron yield with kinetic energy (KE) resolved. We can obtain a mapping of the resonant Auger spectroscopy (mRAS) in the near ambient pressure environment. This approach provides an additional dimension of information along the KE of Auger electrons to reveal details of the valence and unoccupied states at the vicinity of the absorption edge. Complementary to the photoemission spectroscopy that probes the core levels, in situ two-dimension mRAS characterization is useful in studying the electronic structure of complex interfaces of gas-solid and liquid-solid under realistic operating conditions. We herein present the in situ oxidation of Cu(111) in the ambient oxygen environment as demonstration of the mRAS capability. Specifically, resolving the Auger features gives valuable clues to the molecular level understanding of chemical bonding and the evolution of orbital hybridization. In addition, the mRAS results of spatial resolution and mbar range gas pressure are shown and discussed.

Geometric Structure and Electronic Polarization Synergistically Boost Hydrogen Evolution Kinetics in Alkaline Medium.

Efficient electrocatalysts for the hydrogen evolution reaction (HER) are significant for the utilization of hydrogen as a fuel, particularly under alkaline conditions. However, the sluggish kinetics of HER remains a challenge. Here we demonstrate an efficient HER catalyst comprising Ru and AgCl nanoparticles anchored on Ag nanowires (Ru/AgCl@Ag), which delivers a low overpotential of 12 mV at 10 mA cm-2 and a Tafel slope of 38 mV decade-1. A high mass activity of 214 mA mg-1 at an overpotential of 25 mV and a long-term durability in 1.0 M KOH are observed. In combination with computational simulations, we find that the high electronegativity of chlorine in AgCl and d-band electrons from Ru synergistically destabilize the water molecule and modulate H adsorption/desorption on the surface of Ru/AgCl@Ag, respectively. This work opens a promising avenue for the facile design and application of highly active and stable composite electrocatalysts toward water splitting.

Template-free Synthesis of Stable Cobalt Manganese Spinel Hollow Nanostructured Catalysts for Highly Water-Resistant CO Oxidation.

Development of spinel oxides as low-cost and high-efficiency catalysts is highly desirable; however, rational synthesis of efficient and stable spinel systems with precisely controlled structure and components remains challenging. We demonstrate the design of complex nanostructured cobalt-based bimetallic spinel catalysts for low-temperature CO oxidation by a simple template-free method. The self-assembled multi-shelled mesoporous spinel nanostructures provide high surface area (203.5 m2/g) and favorable unique surface chemistry for producing abundant active sites and lead to the creation of robust microsphere configured by 16-nm spinel nanosheets, which achieve satisfactory water-resisting property and catalytic activity. Theoretical models show that O vacancies at exposed {110} facets in cubic spinel phase guarantee the strong adsorption of reactive oxygen species on the surface of catalysts and play a key role in the prevention of deactivation under moisture-rich conditions. The design concept with architecture and composition control can be extended to other mixed transition metal oxide compositions.

Observing the Electrochemical Oxidation of Co Metal at the Solid/Liquid Interface Using Ambient Pressure X-ray Photoelectron Spectroscopy.

Recent advances of ambient pressure X-ray photoelectron spectroscopy (AP-XPS) have enabled the chemical composition and the electrical potential profile at a liquid/electrode interface under electrochemical reaction conditions to be directly probed. In this work, we apply this operando technique to study the surface chemical composition evolution on a Co metal electrode in 0.1 M KOH aqueous solution under various electrical biases. It is found that an ∼12.2 nm-thick layer of Co(OH)2 forms at a potential of about -0.4 VAg/AgCl, and upon increasing the anodic potential to about +0.4 VAg/AgCl, this layer is partially oxidized into cobalt oxyhydroxide (CoOOH). A CoOOH/Co(OH)2 mixture layer is formed on the top of the electrode surface. Finally, the oxidized surface layer can be reduced to Co0 at a cathodic potential of -1.35 VAg/Cl. These observations indicate that the ultrathin layer containing cobalt oxyhydroxide is the active phase for oxygen evolution reaction (OER) on a Co electrode in an alkaline electrolyte, consistent with previous studies.

Theory and Simulation for Traffic Characteristics on the Highway with a Slowdown Section.

We study the traffic characteristics on a single-lane highway with a slowdown section using the deterministic cellular automaton (CA) model. Based on the theoretical analysis, the relationships among local mean densities, velocities, traffic fluxes, and global densities are derived. The results show that two critical densities exist in the evolutionary process of traffic state, and they are significant demarcation points for traffic phase transition. Furthermore, the changing laws of the two critical densities with different length of limit section are also investigated. It is shown that only one critical density appears if a highway is not slowdown section; nevertheless, with the growing length of slowdown section, one critical density separates into two critical densities; if the entire highway is slowdown section, they finally merge into one. The contrastive analysis proves that the analytical results are consistent with the numerical ones.

Using "Tender" X-ray Ambient Pressure X-Ray Photoelectron Spectroscopy as A Direct Probe of Solid-Liquid Interface.

We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a "dip &pull" method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, "dip &pull" approach, with a "tender" X-ray synchrotron source (2 keV-7 keV), we are able to access the interface between liquid and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt(2+) and Pt(4+) interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of "tender" AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.

Influence of Step Geometry on the Reconstruction of Stepped Platinum Surfaces under Coadsorption of Ethylene and CO.

We demonstrate the critical role of the specific atomic arrangement at step sites in the restructuring processes of low-coordinated surface atoms at high adsorbate coverage. By using high-pressure scanning tunneling microscopy (HP-STM) and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), we have investigated the reconstruction of Pt(332) (with (111)-oriented triangular steps) and Pt(557) surfaces (with (100)-oriented square steps) in the mixture of CO and C2H4 in the Torr pressure range at room temperature. CO creates Pt clusters at the step edges on both surfaces, although the clusters have different shapes and densities. A subsequent exposure to a similar partial pressure of C2H4 partially reverts the clusters on Pt(332). In contrast, the cluster structure is barely changed on Pt(557). These different reconstruction phenomena are attributed to the fact that the 3-fold (111)-step sites on Pt(332) allows for adsorption of ethylidyne-a strong adsorbate formed from ethylene-that does not form on the 4-fold (100)-step sites on Pt(557).

Mobility on the reconstructed Pt(100)-hex surface in ethylene and in its mixture with hydrogen and carbon monoxide.

By using high-pressure scanning tunneling microscopy and ambient-pressure X-ray photoelectron spectroscopy, we studied the mobility along with composition, structure and reactivity on the Pt(100)-hex surface. Adsorbates are mobile under 1 Torr of C2H4 and C2H4-H2 mixtures, but adding 3 mTorr of CO quenches the mobility. Ethylene-related adsorbates can also weaken Pt-Pt bonds and thus facilitate displacements in the hexagonal layer.

Properties of disorder-engineered black titanium dioxide nanoparticles through hydrogenation.

The recent discovery of "black" TiO2 nanoparticles with visible and infrared absorption has triggered an explosion of interest in the application of TiO2 in a diverse set of solar energy systems; however, what a black TiO2 nanoparticle really is remains a mystery. Here we elucidate more properties and try to understand the inner workings of black TiO2 nanoparticles with hydrogenated disorders in a surface layer surrounding a crystalline core. Contrary to traditional findings, Ti(3+) here is not responsible for the visible and infrared absorption of black TiO2, while there is evidence of mid-gap states above the valence band maximum due to the hydrogenated, engineered disorders. The hydrogen atoms, on the other hand, can undergo fast diffusion and exchange. The enhanced hydrogen mobility may be explained by the presence of the hydrogenated, disordered surface layer. This unique structure thus may give TiO2, one of the most-studied oxide materials, a renewed potential.