Tuning the surface reactivity of oxides by peroxide species.

The Mars-van Krevelen mechanism is the foundation for oxide-catalyzed oxidation reactions and relies on spatiotemporally separated redox steps. Herein, we demonstrate the tunability of this separation with peroxide species formed by excessively adsorbed oxygen, thereby modifying the catalytic activity and selectivity of the oxide. Using CuO as an example, we show that a surface layer of peroxide species acts as a promotor to significantly enhance CuO reducibility in favor of H2 oxidation but conversely as an inhibitor to suppress CuO reduction against CO oxidation. Together with atomistic modeling, we identify that this opposite effect of the peroxide on the two oxidation reactions stems from its modification on coordinately unsaturated sites of the oxide surface. By differentiating the chemical functionality between lattice oxygen and peroxide, these results are closely relevant to a wide range of catalytic oxidation reactions using excessively adsorbed oxygen to activate lattice oxygen and tune the activity and selectivity of redox sites.

Atomistic Origins of Reversible Noncatalytic Gas-Solid Interfacial Reactions.

Noncatalytic gas-solid reactions are a large group of heterogeneous reactions that are usually assumed to occur irreversibly because of the strong driving force to favor the forward direction toward the product formation. Using the example of Ni oxidation into NiO with CO2, herein, we demonstrate the existence of the reverse element that results in the NiO reduction from the countering effect of the gaseous product of CO. Using in situ electron microscopy observations and atomistic modeling, we show that the oxidation process occurs via preferential CO2 adsorption along step edges that results in step-flow growth of NiO layers, and the presence of Ni atoms on the flat NiO surface promotes the nucleation of NiO layers. Simultaneously, the NiO reduction happens via preferential step-edge adsorption of CO that leads to the receding motion of atomic steps, and the presence of Ni vacancies in the NiO surface facilitates the CO-adsorption-induced surface pitting. Temperature and CO2 pressure effect maps are constructed to illustrate the spatiotemporal dynamics of the competing NiO redox reactions. These results demonstrate the rich gas-solid surface reaction dynamics induced by the coexisting forward and reverse reaction elements and have practical applicability in manipulating gas-solid reactions via controlling the gas environment or atomic structure of the solid surface to steer the reaction toward the desired direction.

Classical and Nonclassical Nucleation and Growth Mechanisms for Nanoparticle Formation.

All solid materials are created via nucleation. In this evolutionary process, nuclei form in solution or at interfaces, expand by monomeric growth and oriented attachment, and undergo phase transformation. Nucleation determines the location and size of nuclei, whereas growth controls the size, shape, and aggregation of newly formed nanoparticles. These physical properties of nanoparticles can affect their functionalities, reactivities, and porosities, as well as their fate and transport. Recent advances in nanoscale analytical technologies allow in situ real-time observations, enabling us to uncover the molecular nature of nuclei and the critical controlling factors for nucleation and growth. Although a single theory cannot yet fully explain such evolving processes, we have started to better understand how both classical andnonclassical theories can work together, and we have begun to recognize the importance of connecting these theories. This review discusses the recent convergence of knowledge about the nucleation and growth of nanoparticles.

Communication Overload in Hospitals: Exploring Organizational Safety Communication, Worker Job Attitudes, and Communication Efficacy.

Hospitals represent complex organizations where a range of hospital workers, from physicians to administrators, encounter a deluge of information they must quickly process and act upon. New technologies implemented to streamline patient care, like electronic health records and wearable technologies, have both enhanced and complicated communicative exchanges between hospital workers and their organizations. Hospital workers feeling over saturated with workplace communication, and thus unable to effectively manage or interpret workplace messages, experience what has been labeled communication overload, which can negatively impact worker productivity and concentration. This study examines hospital workers (N = 303) in a Midwestern U.S. healthcare network, and uses structural equation modeling to offer a preliminary theoretical model that demonstrates the effects and outcomes of communication overload in high-risk organizations. The model offers theoretical implications through depicting communication overload as indirectly related to burnout, job satisfaction, and organizational identification through participation in decision-making and organizational safety climate. Results suggest that even if communication overload is an expected state in high-risk organizations, managers can prevent its negative effects on workers' job attitudes by providing workers opportunities to get involved in organizational decision-making and constructing a robust organizational safety climate. Finally, we suggest pairings of organizational safety communication channels and sources through which high quantities of safety information can be communicated without communicatively overloading workers.

COVID-19 Message Fatigue: How Does It Predict Preventive Behavioral Intentions and What Types of Information are People Tired of Hearing About?

This study examines the impact of message fatigue and what makes people fatigued in the context of the COVID-19 pandemic. Data collected with a Qualtrics panel (N = 744) showed that both active (i.e., reactance) and passive (i.e., inattention) resistance in message processing mediated the relationships between message fatigue and intentions to follow three types of preventive behaviors against COVID-19 (i.e., wearing masks, social distancing, and washing hands). The indirect effect of message fatigue on intention to seek COVID-19 information was explained by inattention but not reactance. Analyses of open-ended responses identified 18 types of COVID-related information that individuals were tired of hearing about. About 73.38% of participants (n = 546) reported that they were tired of hearing about at least one type of information about COVID-19, with mask-wearing being the most frequently mentioned (21.91%). The results extend existing research on message fatigue-evoked resistance to persuasion and provide practical implications for public health message design.

Process-Specific Effects of Sulfate on CaCO3 Formation in Environmentally Relevant Systems.

Additives, such as ions, small molecules, and macromolecules, have been found to regulate the formation of CaCO3 and control its morphologies and properties. However, a single additive usually affects dominantly one process in CaCO3's formation and is seldom found to significantly affect multiple CaCO3 formation processes. Here, we used in situ grazing incidence X-ray techniques to observe the heterogeneous formation of CaCO3 and found that a series of formation processes (i.e., nucleation, growth, and Ostwald ripening) were modulated by sulfate. In the nucleation process, increased interfacial free energy and bulk free energy cooperatively increased the nucleation barrier and decreased nucleation rates. In the growth process, sulfate reduced the electrostatic repulsion between CaCO3 precursors and nuclei, promoting CaCO3 growth. This influence on the growth counteracted the inhibition effect in the nucleation process, causing a nearly 100% increase in the volume of heterogeneously formed CaCO3. Meanwhile, adsorbed sulfate on CaCO3 nuclei may poison the surface of smaller CaCO3 nuclei, inhibiting Ostwald ripening. These revealed sulfate's active roles in controlling CaCO3 formation advance our understanding of sulfate-incorporated biomineralization and scaling phenomena in natural and engineered aquatic environments.

Sulfate-Controlled Heterogeneous CaCO3 Nucleation and Its Non-linear Interfacial Energy Evolution.

Unveiling the effects of an environmental abundant anion "sulfate" on the formation of calcium carbonate (CaCO3) is essential to understand the formation mechanisms of biominerals like corals and brachiopod shells, as well as the scale formation in desalination systems. However, it was experimentally challenging to elucidate the sulfate-CaCO3 interactions at the explicit first step of CaCO3 formation: nucleation. In addition, there is limited quantitative information on the precise control of nucleation kinetics. Here, heterogeneous CaCO3 nucleation is monitored in real time as a function of sulfate concentrations (0-10 mM Na2SO4) using synchrotron-based grazing incidence X-ray scattering techniques. The results showed that sulfate can be incorporated in the nuclei, resulting in a nearly 90% decrease in the CaCO3 nucleation rate, causing a 120% increase in the CaCO3 nucleus size, and inhibiting the vaterite-to-calcite phase transformation. Moreover, this work quantitatively relates sulfate concentrations to the effective interfacial energies of CaCO3 and finds a non-linear trend, suggesting that CaCO3 heterogeneous nucleation is more sensitive at a low sulfate concentration. This study can be readily extended to study other additives and obtain quantitative relationships between additive concentrations and CaCO3 interfacial energies, a key step toward achieving natural and engineered controls on CaCO3 nucleation.

A Social Ties-based Approach to Breast Cancer Patients' Quality of Life: Examining Group Ties and Individual Ties across Offline and Online Settings.

Supportive social ties positively impact cancer patients' health; however, little is known about the intertwined links between both offline and online ties, and individual and group ties. Using the common-identity/common-bond approach, we empirically tested the critical difference that individual and group ties exert on health across offline and online settings. Results from 356 female breast cancer patients showed group ties affect quality of life through sequential group identification and social support, while individual ties affect quality of life through sequential interpersonal bonds and social support. Offline group and online individual ties are stronger predictors of quality of life than online group and offline individual ties. A cluster analysis categorized participants into four distinguishable segments. People with stronger offline interpersonal bonds and online group identification reported a better quality of life. This offers insight into the social dynamics that are most consequential for health, and the potential theoretical pathways through which they operate.

Sending and Receiving Safety and Risk Messages in Hospitals: An Exploration into Organizational Communication Channels and Providers' Communication Overload.

This study explores hospital workers' experiences with workplace communication overload and its implications for effective safety and risk messaging in hospital organizations. We use a multi-step thematic analysis of interview (N = 12) and focus group (N = 8, 28 participants) data collected from hospital workers to analyze how they describe specific organizational communication channels influencing their communication overload. We specifically examine how workers' socially constructed channel affordances and constraints for sending/receiving safety information provide meaning to their communicatively overloaded states. Hospital workers explained that asynchronous channels such as e-mail and voicemail aggravated communication overload, while synchronous channels such as team huddles alleviated it. We discuss the implications of these results for the communication overload model by pointing to violations of communication channel preference and literature on the social affordances of communication channels. Study limitations and future directions are offered.

Reversible oxidation and reduction of gold-supported iron oxide islands at room temperature.

Monolayer iron oxides grown on metal substrates have widely been used as model systems in heterogeneous catalysis. By means of ambient-pressure scanning tunneling microscopy (AP-STM), we studied the in situ oxidation and reduction of FeO(111) grown on Au(111) by oxygen (O2) and carbon monoxide (CO), respectively. Oxygen dislocation lines present on FeO islands are highly active for O2 dissociation. X-ray photoelectron spectroscopy measurements distinctly reveal the reversible oxidation and reduction of FeO islands after sequential exposure to O2 and CO. Our AP-STM results show that excess O atoms can be further incorporated on dislocation lines and react with CO, whereas the CO is not strong enough to reduce the FeO supported on Au(111) that is essential to retain the activity of oxygen dislocation lines.

Quality change mechanism and drinking safety of repeatedly-boiled water and prolonged-boil water: a comparative study.

Quality, safety and potability of repeatedly-boiled water (RBW) and prolonged-boil water (PBW) lead to concern and even misgivings in the public from time to time, especially in China, and other societies have a habit of drinking boiled water, with improvements of living standards and owing to increasing concerns for human health. This phenomenon is mainly attributed to the fact that the conclusions drawn from existing scientific experiments could not respond well to the concerns. In order to make up for this deficiency, tap water was selected to carry out RBW and PBW experiments independently. The quality changes of RBW and PBW show very similar trends that are not as great as might be imagined, and both are impacted by the tap water quality and the physiochemical effects. The dominating physiochemical effects are the water evaporation and the resulting concentration of unreactive components (most dissolved components), which can be easily explained by the existing evaporation-concentration theory. The results show that tap water will be still safe and potable after being frequently boiled or after having undergone prolonged boiling, as long as it satisfies the sanitary standards of drinking water prior to heating. Therefore, there is no need to worry about drinking RBW or PBW in daily life.

Iterative point-wise reinforcement learning for highly accurate indoor visible light positioning.

Iterative point-wise reinforcement learning (IPWRL) is proposed for highly accurate indoor visible light positioning (VLP). By properly updating the height information in an iterative fashion, the IPWRL not only effectively mitigates the impact of non-deterministic noise but also exhibits excellent tolerance to deterministic errors caused by the inaccurate a priori height information. The principle of the IPWRL is explained, and the performance of the IPWRL is experimentally evaluated in a received signal strength (RSS) based VLP system and compared with other positioning algorithms, including the conventional RSS algorithm, the k-nearest neighbors (KNN) algorithm and the PWRL algorithm where iterations exclude. Unlike the supervised machine learning method, e.g., the KNN, whose performance is highly dependent on the training process, the proposed IPWRL does not require training and demonstrates robust positioning performance for the entire tested area. Experimental results also show that when a large height information mismatch occurs, the IPWRL is able to first correct the height information and then offers robust positioning results with a rather low positioning error, while the positioning errors caused by the other algorithms are significantly higher.

Effects of sulfate on biotite interfacial reactions under high temperature and high CO2 pressure.

To ensure the safety and efficiency of engineered subsurface operations, it is vital to understand impacts of aqueous chemistries on brine-mineral interactions in subsurface environments. In this study, using biotite as a model phyllosilicate, we investigated the effects of sulfate on its interfacial reactions under subsurface relevant conditions (95 °C and 102 atm of CO2). By making monodentate mononuclear complexes with biotite surface sites, 50 mM sulfate enhanced biotite dissolution by 40% compared to that without sulfate. However, sulfate at lower concentrations than 50 mM did not obviously affect biotite dissolution. In addition, sulfate did not impact secondary mineral precipitation. However, even without any discernible surface morphological change, sulfate adsorption made biotite surfaces more hydrophilic. To provide a more comprehensive perspective on environmentally-abundant ligands, we further comparatively examined the effects of various inorganic (e.g., sulfate and phosphate) and organic ligands (e.g., acetate, oxalate, and phosphonates) on biotite interfacial interactions and assessed their impacts on physico-chemical properties. We found that the presence of phosphate and phosphonates significantly promoted precipitation of Fe- and Al-bearing secondary minerals, but sulfate, acetate, and oxalate did not. Biotite surface wettability was also altered as a result of changes in biotite surface functional groups and surface charges by ligand adsorption: sulfate, oxalate, phosphate, and phosphonate made biotite more hydrophilic, while acetate made it less hydrophilic. This study provides useful new insights into the effects of brine chemistries on brine-mineral interactions, enabling safer and more efficient engineered subsurface operations.

Superpixel Segmentation Based Synthetic Classifications with Clear Boundary Information for a Legged Robot.

In view of terrain classification of the autonomous multi-legged walking robots, two synthetic classification methods for terrain classification, Simple Linear Iterative Clustering based Support Vector Machine (SLIC-SVM) and Simple Linear Iterative Clustering based SegNet (SLIC-SegNet), are proposed. SLIC-SVM is proposed to solve the problem that the SVM can only output a single terrain label and fails to identify the mixed terrain. The SLIC-SegNet single-input multi-output terrain classification model is derived to improve the applicability of the terrain classifier. Since terrain classification results of high quality for legged robot use are hard to gain, the SLIC-SegNet obtains the satisfied information without too much effort. A series of experiments on regular terrain, irregular terrain and mixed terrain were conducted to present that both superpixel segmentation based synthetic classification methods can supply reliable mixed terrain classification result with clear boundary information and will put the terrain depending gait selection and path planning of the multi-legged robots into practice.

"Social Networkout": Connecting Social Features of Wearable Fitness Trackers with Physical Exercise.

Despite widespread understanding of the benefits of physical activity, many adults in the United States do not meet recommended exercise guidelines. Burgeoning technologies, including wearable fitness trackers (e.g., Fitbit, Apple watch), bring new opportunities to influence physical activity by encouraging users to track and share physical activity data and compete against their peers. However, research has not explored the social processes that mediate the relationship between the use of wearable fitness trackers and intention to exercise. In this study, we applied the Theory of Planned Behavior (Ajzen, 1991) to explore the effects of two communicative features of wearable fitness devices-social sharing and social competing-on individuals' intention to exercise. Drawing upon surveys from 238 wearable fitness tracker users, we found that the relationship between the two communication features (social sharing and competing) and exercise intention was mediated by attitudes, subjective norms, and perceived behavioral control. The results suggest that the ways in which exercise data are shared significantly influence the exercise intentions, and these intentions are mediated by individuals' evaluation of exercise, belief about important others' approval of exercise, and perceived control upon exercise.

Communicating Health at Work: Organizational Wellness Programs as Identity Bridges.

With the growth in workplace health promotion (WHP) initiatives, organizations are asking employees to enact their personal health identities at work. To understand this prominent yet poorly understood phenomenon, we surveyed 204 employees at a company with a WHP program and found that participation in the wellness program mediated personal health and organizational identities. Results fill a gap in communication literature by demonstrating the effect of individual identity enactment on organizational identification and contribute to recent research stressing the relationship between identity and health behaviors. In addition, findings illuminate the role of situated activity in identity negotiation, suggesting that certain activities in organizations, like wellness programs, serve as identity bridges between personal and work-related identity targets.

Turning and Radius Deviation Correction for a Hexapod Walking Robot Based on an Ant-Inspired Sensory Strategy.

Abstract: In order to find a common approach to plan the turning of a bio-inspired hexapod robot, a locomotion strategy for turning and deviation correction of a hexapod walking robot based on the biological behavior and sensory strategy of ants. A series of experiments using ants were carried out where the gait and the movement form of ants was studied. Taking the results of the ant experiments as inspiration by imitating the behavior of ants during turning, an extended turning algorithm based on arbitrary gait was proposed. Furthermore, after the observation of the radius adjustment of ants during turning, a radius correction algorithm based on the arbitrary gait of the hexapod robot was raised. The radius correction surface function was generated by fitting the correction data, which made it possible for the robot to move in an outdoor environment without the positioning system and environment model. The proposed algorithm was verified on the hexapod robot experimental platform. The turning and radius correction experiment of the robot with several gaits were carried out. The results indicated that the robot could follow the ideal radius and maintain stability, and the proposed ant-inspired turning strategy could easily make free turns with an arbitrary gait.

Trajectory Correction and Locomotion Analysis of a Hexapod Walking Robot with Semi-Round Rigid Feet.

Aimed at solving the misplaced body trajectory problem caused by the rolling of semi-round rigid feet when a robot is walking, a legged kinematic trajectory correction methodology based on the Least Squares Support Vector Machine (LS-SVM) is proposed. The concept of ideal foothold is put forward for the three-dimensional kinematic model modification of a robot leg, and the deviation value between the ideal foothold and real foothold is analyzed. The forward/inverse kinematic solutions between the ideal foothold and joint angular vectors are formulated and the problem of direct/inverse kinematic nonlinear mapping is solved by using the LS-SVM. Compared with the previous approximation method, this correction methodology has better accuracy and faster calculation speed with regards to inverse kinematics solutions. Experiments on a leg platform and a hexapod walking robot are conducted with multi-sensors for the analysis of foot tip trajectory, base joint vibration, contact force impact, direction deviation, and power consumption, respectively. The comparative analysis shows that the trajectory correction methodology can effectively correct the joint trajectory, thus eliminating the contact force influence of semi-round rigid feet, significantly improving the locomotion of the walking robot and reducing the total power consumption of the system.

The Roles of Oil-Water Interfaces in Forming Ultrasmall CaSO4 Nanoparticles.

In natural and engineered environmental systems, calcium sulfate (CaSO4) nucleation commonly occurs at dynamic liquid-liquid interfaces. Although CaSO4 is one of the most common minerals in oil spills and oil-water separation, the mechanisms driving its nucleation at these liquid-liquid interfaces remain poorly understood. In this study, using in situ small-angle X-ray scattering (SAXS), we examined CaSO4 nucleation at oil-water interfaces and found that within 60 minutes of reaction, short rod-shaped nanoparticles (with a radius of gyration (Rg) of 17.2 ± 2.7 nm and a length of 38.2 ± 5.8 nm) had formed preferentially at the interfaces. Wide-angle X-ray scattering (WAXS) analysis identified these nanoparticles as gypsum (CaSO4·2H2O). In addition, spherial nanoparticles measuring 4.1 nm in diameter were observed at oil-water interfaces, where surface-enhanced Raman spectroscopy (SERS) revealed an elevated pH compared to the bulk solution. The negatively charged oil-water interfaces preferentially adsorb calcium ions, collectively promoting CaSO4 formation there. CaSO4 particle formation at the oil-water interface follows a nonclassical nucleation (N-CNT) pathway by forming ultrasmall amorphous spherical particles which then aggregate to form intermediate nanoparticles, subsequently growing into nanorod-shaped gypsum. These findings of this study provide insights into mineral scaling during membrane separation and can inform more efficient oil transport in energy recovery systems.

Generic Mechanism for Waveform Regulation and Synchronization of Oscillators: An Application for Robot Behavior Diversity Generation.

While nonlinear oscillators have been widely used for central pattern generators to produce basic rhythmic signals for robot locomotion control, methods to shape and regulate the signal waveform without changing the characteristics of the oscillators have not been fully investigated, especially during the network synchronization process. To illustrate the principle and process of waveform regulation of nonlinear oscillators in detail and ensure that the influence can be controlled, we present a method for waveform regulation and synchronization and analyze the relationship of different factors (e.g., initial conditions, network parameters, phase, and waveform regulation factors) in synchronization deviation. Then, the method is indicated to be effective in other commonly used nonlinear oscillators and neural oscillators. As an example application, a three-layer behavioral control architecture for a legged robot is constructed based on the proposed method. Modules for the body behavior, leg coordination, and single-leg adjustment are established to realize diverse robot behaviors. The effectiveness of the method is validated by a series of experiments. The results prove that the method performs well in terms of signal control accuracy, behavior pattern diversity, and smooth motion transition.