Steering CO2 hydrogenation toward C-C coupling to hydrocarbons using porous organic polymer/metal interfaces.

The conversion of CO2 into fuels and chemicals is an attractive option for mitigating CO2 emissions. Controlling the selectivity of this process is beneficial to produce desirable liquid fuels, but C-C coupling is a limiting step in the reaction that requires high pressures. Here, we propose a strategy to favor C-C coupling on a supported Ru/TiO2 catalyst by encapsulating it within the polymer layers of an imine-based porous organic polymer that controls its selectivity. Such polymer confinement modifies the CO2 hydrogenation behavior of the Ru surface, significantly enhancing the C2+ production turnover frequency by 10-fold. We demonstrate that the polymer layers affect the adsorption of reactants and intermediates while being stable under the demanding reaction conditions. Our findings highlight the promising opportunity of using polymer/metal interfaces for the rational engineering of active sites and as a general tool for controlling selective transformations in supported catalyst systems.

Reduction of Cofed Carbon Dioxide Modifies the Local Coordination Environment of Zeolite-Supported, Atomically Dispersed Chromium to Promote Ethane Dehydrogenation.

The reduction of CO2 is known to promote increased alkene yields from alkane dehydrogenations when the reactions are cocatalyzed. The mechanism of this promotion is not understood in the context of catalyst active-site environments because CO2 is amphoteric, and even general aspects of the chemistry, including the significance of competing side reactions, differ significantly across catalysts. Atomically dispersed chromium cations stabilized in highly siliceous MFI zeolite are shown here to enable the study of the role of parallel CO2 reduction during ethylene-selective ethane dehydrogenation. Based on infrared spectroscopy and X-ray absorption spectroscopy data interpreted through calculations using density functional theory (DFT), the synthesized catalyst contains atomically dispersed Cr cations stabilized by silanol nests in micropores. Reactor studies show that cofeeding CO2 increases stable ethylene-selective ethane dehydrogenation rates over a wide range of partial pressures. Operando X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) spectra indicate that during reaction at 650 °C the Cr cations maintain a nominal 2+ charge and a total Cr-O coordination number of approximately 2. However, CO2 reduction induces a change, correlated with the CO2 partial pressure, in the population of two distinct Cr-O scattering paths. This indicates that the promotional effect of parallel CO2 reduction can be attributed to a subtle change in Cr-O bond lengths in the local coordination environment of the active site. These insights are made possible by simultaneously fitting multiple EXAFS spectra recorded in different reaction conditions; this novel procedure is expected to be generally applicable for interpreting operando catalysis EXAFS data.

Daily Fluctuations in Adolescents' Perceived Friend Dominance and Friendship Clout: Associations with Mood and the Moderating Role of Anxiety.

Emerging evidence suggests that whereas occupying high peer status promotes adolescents' well-being, feeling dominated by friends confers psychological costs. However, little is known about day-to-day power dynamics of adolescents' friendships or their acute affective consequences. This 14-day intensive longitudinal study introduced novel daily assessments of friend dominance and friendship clout, examined their associations with mood, and tested anxiety as a moderator. Participants were 195 11th-graders (Mage = 16.48, SDage = 0.35; 66% female). Multilevel models revealed that adolescents experienced worse mood on days they felt dominated by friends and better mood on days they felt powerful and influential among friends. Associations with negative mood were strongest for adolescents higher in anxiety. The findings underscore the dynamic nature of power in adolescents' friendships.

Reciprocal Associations Between Science Efficacy, STEM Identity and Scientist Career Interest Among Adolescent Girls within the Context of Informal Science Learning.

Limited research has explored the longitudinal pathway to youth career interests via identity and efficacy together. This study examined the longitudinal associations between science efficacy, STEM (science, technology, engineering and math) identity, and scientist career interest among girls who are historically considered as an underrepresented group among scientists. The sample included 308 girls (M age = 15.22, SD age = 1.66; 42.8% White) from six STEM youth programs, each at a different informal science learning site within the U.K. and the U.S. Longitudinal structural equation modelling demonstrated that science efficacy consistently predicted STEM identity and scientist career interest, and similarly, STEM identity consistently predicted science efficacy over a two-year period. Scientist career interest at 12 months predicted science efficacy at 24 months. The coefficients of efficacy predicting STEM identity and scientist career interest were significantly larger compared to STEM identity and scientist career interest in predicting science efficacy from 12 months to 24 months. Further mediation analysis supported a significant pathway from STEM identity at 3 months to scientist career interest at 24 months via 12-month science efficacy. The findings highlight that science efficacy and STEM identity for girls relate to their scientist career interest and these longitudinal associations are reciprocal. This study suggests that science efficacy and STEM identity mutually influence each other, and enhancing science efficacy and STEM identity is key to promoting adolescents' interest in being a scientist.

Developmental Trajectories of Adolescents' Math Motivation: The Role of Mindset and Perceptions of Informal STEM Learning Site Inclusivity.

Motivation is a key factor in engagement, achievement, and career choices in science, technology, engineering, and mathematics (STEM). While existing research has focused on student motivation toward math in formal school programs, new work is needed that focuses on motivation for those involved in informal STEM programs. Specifically, the role of math mindset and perceived inclusivity of informal STEM sites (to those of varying gender and ethnic backgrounds) on longitudinal trajectories of adolescents' math motivation has not been explored. This study investigates longitudinal changes in math expectancy, interest, and utility values and the effects of math fixed mindset, math growth mindset, and perceptions of the inclusivity of informal STEM learning sites on these changes for adolescents participating in STEM programs at these informal sites in the United Kingdom and the United States (n = 249, MT1age = 15.2, SD = 1.59). Three latent growth curve models were tested. The data suggest that math expectancy, interest, and utility values declined over three years. Growth mindset positively predicted changes in utility, while fixed mindset negatively predicted changes in utility. Inclusivity positively influenced the initial levels of utility. Girls reported lower initial expectancy than boys. Age influenced both the initial levels and rate of change for expectancy. Older adolescents had lower levels of expectancy compared to their younger counterparts; however, they had a less steep decline in expectancy over three years. These findings suggest that designing inclusive learning environments and promoting growth mindset may encourage math motivation.

Structure and Site Evolution of Framework Ni Species in MIL-127 MOFs for Propylene Oligomerization Catalysis.

A mixed-valence oxotrimer metal-organic framework (MOF), Ni-MIL-127, with a fully coordinated nickel atom and two iron atoms in the inorganic node, generates a missing linker defect upon thermal treatment in helium (>473 K) to engender an open coordination site on nickel which catalyzes propylene oligomerization devoid of any cocatalysts or initiators. This catalyst is stable for ∼20 h on stream at 500 kPa and 473 K, unprecedented for this chemistry. The number of missing linkers on synthesized and activated Ni-MIL-127 MOFs is quantified using temperature-programmed oxidation, 1H nuclear magnetic resonance spectroscopy, and X-ray absorption spectroscopy to be ∼0.7 missing linkers per nickel; thus, a majority of Ni species in the MOF framework catalyze propylene oligomerization. In situ NO titrations under reaction conditions enumerate ∼62% of the nickel atoms as catalytically relevant to validate the defect density upon thermal treatment. Propylene oligomerization rates on Ni-MIL-127 measured at steady state have activation energies of 55-67 kJ mol-1 from 448 to 493 K and are first-order in propylene pressures from 5 to 550 kPa. Density functional theory calculations on cluster models of Ni-MIL-127 are employed to validate the plausibility of the missing linker defect and the Cossee-Arlman mechanism for propylene oligomerization through comparisons between apparent activation energies from steady-state kinetics and computation. This study illustrates how MOF precatalysts engender defective Ni species which exhibit reactivity and stability characteristics that are distinct and can be engineered to improve catalytic activity for olefin oligomerization.

Dynamic Evolution of Palladium Single Atoms on Anatase Titania Support Determines the Reverse Water-Gas Shift Activity.

Research interest in single-atom catalysts (SACs) has been continuously increasing. However, the lack of understanding of the dynamic behaviors of SACs during applications hinders catalyst development and mechanistic understanding. Herein, we report on the evolution of active sites over Pd/TiO2-anatase SAC (Pd1/TiO2) in the reverse water-gas shift (rWGS) reaction. Combining kinetics, in situ characterization, and theory, we show that at T ≥ 350 °C, the reduction of TiO2 by H2 alters the coordination environment of Pd, creating Pd sites with partially cleaved Pd-O interfacial bonds and a unique electronic structure that exhibit high intrinsic rWGS activity through the carboxyl pathway. The activation by H2 is accompanied by the partial sintering of single Pd atoms (Pd1) into disordered, flat, ∼1 nm diameter clusters (Pdn). The highly active Pd sites in the new coordination environment under H2 are eliminated by oxidation, which, when performed at a high temperature, also redisperses Pdn and facilitates the reduction of TiO2. In contrast, Pd1 sinters into crystalline, ∼5 nm particles (PdNP) during CO treatment, deactivating Pd1/TiO2. During the rWGS reaction, the two Pd evolution pathways coexist. The activation by H2 dominates, leading to the increasing rate with time-on-stream, and steady-state Pd active sites similar to the ones formed under H2. This work demonstrates how the coordination environment and nuclearity of metal sites on a SAC evolve during catalysis and pretreatments and how their activity is modulated by these behaviors. These insights on SAC dynamics and the structure-function relationship are valuable to mechanistic understanding and catalyst design.

Genesis of Active Pt/CeO2 Catalyst for Dry Reforming of Methane by Reduction and Aggregation of Isolated Platinum Atoms into Clusters.

Atomically dispersed metal catalysts offer the advantages of efficient metal utilization and high selectivities for reactions of technological importance. Such catalysts have been suggested to be strong candidates for dry reforming of methane (DRM), offering prospects of high selectivity for synthesis gas without coke formation, which requires ensembles of metal sites and is a challenge to overcome in DRM catalysis. However, investigations of the structures of isolated metal sites on metal oxide supports under DRM conditions are lacking, and the catalytically active sites remain undetermined. Data characterizing the DRM reaction-driven structural evolution of a cerium oxide-supported catalyst, initially incorporating atomically dispersed platinum, and the corresponding changes in catalyst performance are reported. X-ray absorption and infrared spectra show that the reduction and agglomeration of isolated cationic platinum atoms to form small platinum clusters/nanoparticles are necessary for DRM activity. Density functional theory calculations of the energy barriers for methane dissociation on atomically dispersed platinum and on platinum clusters support these observations. The results emphasize the need for in-operando experiments to assess the active sites in such catalysts. The inferences about the catalytically active species are suggested to pertain to a broad class of catalytic conversions involving the rate-limiting dissociation of light alkanes.

CatMass: software for calculating optimal sample masses for X-ray absorption spectroscopy experiments involving complex sample compositions.

This paper presents software for calculating the optimal mass of samples with complex compositions (e.g. supported metal catalysts) for X-ray absorption spectroscopy (XAS) and scattering measurements. The ability to calculate the sample mass and other relevant parameters needed for an XAS measurement allows experimentalists to be better prepared in terms of detector selection, energy range of scan and overall time needed to complete the measurement, thus increasing efficiency. CatMass builds on existing sample mass calculators allowing users to determine the optimum sample preparation, collection geometry, usable energy range for a scan and approximate edge step of the absorption event. Visualization tools present the absorption calculation results in a format familiar to XAS experimentalists, with the added ability to save calculations and plots for future reference or recalculation. CatMass is a program broadly applicable in catalysis and is helpful for users with complex samples due to composition/stoichiometry or multiple competing elements.

Templated encapsulation of platinum-based catalysts promotes high-temperature stability to 1,100 °C.

Stable catalysts are essential to address energy and environmental challenges, especially for applications in harsh environments (for example, high temperature, oxidizing atmosphere and steam). In such conditions, supported metal catalysts deactivate due to sintering-a process where initially small nanoparticles grow into larger ones with reduced active surface area-but strategies to stabilize them can lead to decreased performance. Here we report stable catalysts prepared through the encapsulation of platinum nanoparticles inside an alumina framework, which was formed by depositing an alumina precursor within a separately prepared porous organic framework impregnated with platinum nanoparticles. These catalysts do not sinter at 800 °C in the presence of oxygen and steam, conditions in which conventional catalysts sinter to a large extent, while showing similar reaction rates. Extending this approach to Pd-Pt bimetallic catalysts led to the small particle size being maintained at temperatures as high as 1,100 °C in air and 10% steam. This strategy can be broadly applied to other metal and metal oxides for applications where sintering is a major cause of material deactivation.

Aqueous Structure of Lanthanide-EDTA Coordination Complexes Determined by a Combined DFT/EXAFS Approach.

Sustainable production of rare earth elements (REEs) is critical for technologies needed for climate change mitigation, including wind turbines and electric vehicles. However, separation technologies currently used in REE production have large environmental footprints, necessitating more sustainable strategies. Aqueous, affinity-based separations are examples of such strategies. To make these technologies feasible, it is imperative to connect aqueous ligand structure to ligand selectivity for individual REEs. As a step toward this goal, we analyzed the extended X-ray absorption fine structure (EXAFS) of four lanthanides (La, Ce, Pr, and Nd) complexed by a common REE chelator, ethylenediaminetetraacetic acid (EDTA) to determine the aqueous-phase structure. Reference structures from density functional theory (DFT) were used to help fit the EXAFS spectra. We found that all four Ln-EDTA coordination complexes formed 9-coordinate structures with 6 coordinating atoms from EDTA (4 carboxyl oxygen atoms and 2 nitrogen atoms) and 3 oxygen atoms from water molecules. All EXAFS fits were of high quality (R-factor < 0.02) and showed decreasing average first-shell coordination distance across the series (2.62-2.57 Å from La-Nd), in agreement with DFT (2.65-2.56 Å from La-Nd). The insights determined herein will be useful in the development of ligands for sustainable rare earth elements (REE) separation technologies.

Peer victimization, schooling format, and adolescent internalizing symptoms during the COVID-19 pandemic: Between- and within-person associations across ninth grade.

The current longitudinal study examined how between-person (BP) differences and within-person (WP) fluctuations in adolescents' peer victimization and schooling format across ninth grade related to changes in their internalizing symptoms during the COVID-19 pandemic. Participants were 388 adolescents (61% female; M age = 14.02) who completed three online surveys, administered 3 months apart, from November 2020 to May 2021. Multilevel modeling revealed BP (time-invariant) and WP (time-varying) effects of peer victimization and school instructional format (i.e., in-person; hybrid; online) on internalizing symptoms while accounting for potentially confounding demographic (e.g., gender) and contextual (e.g., COVID-19 positivity rates) factors. Results indicated that adolescents who experienced higher overall levels of peer victimization across the school year, compared to those who experienced lower victimization, reported more severe internalizing symptoms. Whereas relative WP increases in peer victimization predicted corresponding increases in adolescents' depressive and somatic symptoms regardless of schooling format, WP increases in peer victimization only predicted elevated anxiety during months when students attended fully in-person, but not online, school. Adolescents who spent a greater proportion of their school year attending online school also reported less peer victimization across the year. Findings highlight WP fluctuations in the effects of peer victimization on internalizing and contextual variations depending on schooling format.

The Power Dynamics of Friendship: Between- and Within- Person Associations among Friend Dominance, Self-Esteem, and Adolescent Internalizing Symptoms.

Although forming close, egalitarian peer relationships is a central developmental task of adolescence, little is known about the psychological consequences of power imbalances in adolescents' friendships. The current study investigated whether there are psychological costs of feeling subordinate to friends by examining longitudinal associations between adolescents' perceived friend dominance and internalizing symptoms. Across one year, five waves of survey data were collected from 388 adolescents (Mage = 14.05, SDage = 0.41; 61% female; 46% White, 19% Black, 17% Asian, 6% Arab, Middle Eastern, North African, 6% Biracial/Multiethnic, 3% Latinx/Hispanic, 1% American Indian/Native American, 1% identifying with another race/ethnicity, <1% not reporting). Multilevel modeling disentangled between- and within-person effects of perceived friend dominance on depressive and anxiety (internalizing) symptoms and tested self-esteem as a mediator. The results indicated that both individual differences and intraindividual fluctuations in perceived friend dominance were associated with internalizing symptoms. At the between-person level, adolescents who perceived their friends as more dominant reported more severe depressive and anxiety symptoms than adolescents who perceived their friends as less dominant. At the within-person level, increases in perceived friend dominance were accompanied by increases in depressive and anxiety symptoms, and these associations were partially explained by changes in self-esteem. The findings advance understanding of power dynamics in adolescents' close friendships and highlight the psychological toll of feeling dominated by friends.

Promoting Diverse Youth's Career Development through Informal Science Learning: The Role of Inclusivity and Belonging.

Little research has examined the associations between perceived inclusivity within informal science learning sites, youth program belonging and perceptions of program career preparation. This study explored relations between these factors at three timepoints (T1 = start of program, T2 = 3 months and T3 = 12 months after start). Participants were a diverse sample of 209 adolescents participating in STEM youth programs within informal science learning sites situated in the United States and United Kingdom (70% females: M age = 15.27, SD age = 1.60), with 53.1% British and 64.1% non-White. Path analysis revealed that only perceptions of inclusivity for own social identity group (i.e., gender, ethnicity) at T1 were associated with T2 STEM youth program belonging. There was a significant indirect effect of T1 perceptions of inclusivity for one's own social identity groups on T3 perceptions of program career preparation via T2 program belonging. This study highlights that, over time, perceptions of inclusivity around youth's own social identity groups (i.e., gender and ethnicity/culture) are related to a sense of youth program belonging, which in turn is later associated with perceptions of program career preparation.

Interest, Mindsets and Engagement: Longitudinal Relations in Science Orientations for Adolescents in Informal Science Programs.

Little is known about the factors that influence engagement for adolescents participating in informal youth science programs. This study examined longitudinal reciprocal associations between adolescents' science engagement, interest, and growth mindset. Participants were adolescents (Mage = 15.06, SD = 1.82 years, 66.8% female) from the UK (n = 168) and the US (n = 299). A cross lagged path analysis indicated that participants' science growth mindset at baseline was positively related to interest, and engagement at year 1, and science interest at year 1 was positively related to growth mindset at year 2. Additionally, girls had lower science growth mindsets than boys. This evidence suggests that informal programs may encourage positive STEM trajectories by fostering engagement, growth mindset and interest.

Preparing the Next Generation for STEM: Adolescent Profiles Encompassing Math and Science Motivation and Interpersonal Skills and Their Associations With Identity and Belonging.

Science, technology, engineering, and math (STEM) workers need both motivation and interpersonal skills in STEM disciplines. The aims of the study were to identify clusters of adolescents who vary in math and science motivation and interpersonal skills and to explore what factors are related to membership in a high math and science motivation and interpersonal skills cluster. Participants included 467 adolescents (312 female; Mage = 15.12 to SD = 1.71 year) recruited from out-of-school STEM programs in the US and UK. Findings from latent class analyses revealed four clusters, including a "High Math and Science Motivation and Interpersonal Skills" group, as well as groups that exhibited lower levels of either motivation or interpersonal skills. STEM program belonging, and STEM identity are related to membership in the high motivation and skills cluster. Findings provide insight into factors that may encourage motivation and interpersonal skills in adolescents, preparing them for STEM workforce entry.

Epidemiologic, Immunologic, and Virus Characteristics in Patients With Paired Severe Acute Respiratory Syndrome Coronavirus 2 Serology and Reverse-Transcription Polymerase Chain Reaction Testing.

BACKGROUND: The natural history and clinical progression of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infections can be better understood using combined serological and reverse-transcription polymerase chain reaction (RT-PCR) testing. METHODS: Nasopharyngeal swabs and serum were collected at a single time-point from patients at an urban, public hospital during August-November 2020 and tested for SARS-CoV-2 using RT-PCR, viral culture, and anti-spike pan-immunoglobulin antibody testing. Participant demographics and symptoms were collected through interview. The χ 2 and Fisher exact tests were used to identify associations between RT-PCR and serology results with presence of viable virus and frequency of symptoms. RESULTS: Among 592 participants, 129 (21.8%) had evidence of SARS-CoV-2 infection by RT-PCR or serology. Presence of SARS-CoV-2 antibodies was strongly associated with lack of viable virus (P = .016). COVID-19 symptom frequency was similar for patients testing RT-PCR positive/seronegative and patients testing RT-PCR positive/seropositive. Patients testing RT-PCR positive/seronegative reported headaches, fatigue, diarrhea, and vomiting at rates not statistically significantly different from those testing RT-PCR negative/seropositive. CONCLUSIONS: While patients testing SARS-CoV-2 seropositive were unlikely to test positive for viable virus and were therefore at low risk for forward transmission, coronavirus disease 2019 (COVID-19) symptoms were common. Paired SARS-CoV-2 RT-PCR and antibody testing provides more nuanced understanding of patients' COVID-19 status.

Size-Dependent Dispersion of Rhodium Clusters into Isolated Single Atoms at Low Temperature and the Consequences for CO Oxidation Activity.

Understanding the dynamic structural evolution of supported metal clusters under reaction conditions is crucial to develop structure reactivity relations. Here, we followed the structure of different size Rh clusters supported on Al2 O3 using in situ/operando spectroscopy and ex situ aberration-corrected electron microscopy. We report a dynamic evolution of rhodium clusters into thermally stable isolated single atoms upon exposure to oxygen and during CO oxidation. Rh clusters partially disperse into single atoms at room temperature and the extent of dispersion increases as the Rh size decreases and as the reaction temperature increases. A strong correlation is found between the extent of dispersion and the CO oxidation kinetics. More importantly, dispersing Rh clusters into single atoms increases the activity at room temperature by more than two orders of magnitude due to the much lower activation energy on single atoms (40 vs. 130 kJ/mol). This work demonstrates that the structure and reactivity of small Rh clusters are very sensitive to the reaction environment.

Catalytic Performance and Near-Surface X-ray Characterization of Titanium Hydride Electrodes for the Electrochemical Nitrate Reduction Reaction.

The electrochemical nitrate reduction reaction (NO3RR) on titanium introduces significant surface reconstruction and forms titanium hydride (TiHx, 0 < x ≤ 2). With ex situ grazing-incidence X-ray diffraction (GIXRD) and X-ray absorption spectroscopy (XAS), we demonstrated near-surface TiH2 enrichment with increasing NO3RR applied potential and duration. This quantitative relationship facilitated electrochemical treatment of Ti to form TiH2/Ti electrodes for use in NO3RR, thereby decoupling hydride formation from NO3RR performance. A wide range of NO3RR activity and selectivity on TiH2/Ti electrodes between -0.4 and -1.0 VRHE was observed and analyzed with density functional theory (DFT) calculations on TiH2(111). This work underscores the importance of relating NO3RR performance with near-surface electrode structure to advance catalyst design and operation.

On shaky grounds: Peer victimization predicts friendship instability across the ninth grade school year.

INTRODUCTION: Although prior research has considered how friendship quality or quantity influence peer victimization risk and vice versa, considerably less is known about how friendship instability (i.e., high levels of friend turnover) and peer victimization may be related to each other across time. METHODS: Survey data were collected from 9th grade students (N = 388; Mage = 14.05; 60.60% female; 35.8% male; 1.8% non-binary; 1.9% trans/unsure/something else) across 3-month intervals spanning one school year. Using cross-lagged panel modeling, this study investigated cross-lagged longitudinal associations between friendship instability and peer victimization utilizing three waves of data collected across one academic year. RESULTS: Adolescents experiencing greater peer victimization at the beginning of the school year were more likely to experience friendship instability by the end of the school year. However, friendship instability at the beginning of the school year was unrelated to subsequent peer victimization. CONCLUSION: Peer victimized adolescents are less likely than their nonvictimized peers to maintain stable friendships over time. Findings suggest that adolescents who are victimized by peers after transitioning to high school may have difficulty maintaining friendships.