Insightful Understanding of Synergistic Oxygen Reduction on PtCo3(111) Toward Zinc-Air Batteries.

Theory-guided materials design is an effective strategy for designing catalysts with high intrinsic activity whilst minimizing the usage of expensive metals like platinum. As proof-of-concept, herein it demonstrates that using density functional theory (DFT) calculations and experimental validation that intermetallic PtCo3 alloy nanoparticles offer enhanced electrocatatalytic performance for the oxygen reduction reaction (ORR) compared to Pt nanoparticles. DFT calculations established that PtCo3(111) surfaces possess better intrinsic ORR activity compared to Pt(111) surfaces, owing to the synergistic action of adjacent Pt and Co active sites which optimizes the binding strength of ORR intermediates to boost overall ORR kinetics. With this understanding, a PtCo3/NC catalyst, comprising PtCo3 nanoparticles exposing predominantly (111) facets dispersed on an N-doped carbon support, is successfully fabricated. PtCo3/NC demonstrates a high specific activity (3.4 mA cm-2 mgPt -1), mass activity (0.67 A mgPt -1), and cycling stability for the ORR in 0.1 M KOH, significantly outperforming a commercial 20 wt.% Pt/C catalyst. Moreover, a zinc-air battery (ZAB) assembled with PtCo3/NC as the air-electrode catalyst delivered an open-circuit voltage of 1.47 V, a specific capacity of 775.1 mAh gZn -1 and excellent operation durability after 200 discharge/charge cycles, vastly superior performance to a ZAB built using commercial Pt/C+IrO2 as the air-electrode catalyst.

Improving the Performance of Pd for Formic Acid Dehydrogenation by Introducing Barium Titanate.

Formic acid, a safe and widely available organic compound, produces hydrogen under mild conditions, with the existence of Pd-based catalysts. Efficiently generating hydrogen via formic acid decomposition (FAD) is restricted by the cleavage of the C-H bond in adsorbed HCOO* and strong adsorption of hydrogen on the Pd surface. Herein, tetragonal-phase barium titanate (TBT) was in situ grown on reduced graphene oxide (rGO) to support Pd (Pd/TBT/rGO) for FAD. The internal electric field exists around TBT owing to its spontaneous polarization capacity. The physical characterizations illustrate that the introduction of barium titanate affects the catalytic performance of the catalyst by decreasing the particle size of Pd nanoparticles (NPs) and forming electron-rich Pd. The as-synthesized Pd/TBT/rGO exhibited excellent catalytic activity and hydrogen selectivity for FAD with a high initial turnover frequency up to 3019.72 h-1 at 333 K. The reason for this enhancement is not only the small-size Pd NPs but also the internal electric field from TBT, which promotes the desorption of adsorbed hydrogen on the Pd surface. Additionally, the electron-rich Pd is favorable to the cleavage of the C-H bond in HCOO*. This work will improve the understanding of the characterization of barium titanate and provide a new design strategy for the FAD catalyst.

Carbon-coated silica supported palladium for hydrogen production from formic acid - Exploring the influence of strong metal support interaction.

Hydrogen energy is one of the most promising energy carriers to solve the increasingly severe energy crisis. Formic acid decomposition (FAD) solves the storage and transportation problems of hydrogen gas since hydrogen can be produced from aqueous formic acid under mild conditions. To efficiently convert formic acid to hydrogen gas, chemical and structural modification of Pd nanoparticles or supports have been carried out, especially introducing the strong metal support interaction (SMSI). Herein, we synthesized core-shell structured SiO2@SC compounds as the supports to introduce SMIS to Pd/PdO nanoparticles. The relationship between FAD activity and SMSI is investigated. The SMSI between Pd/PdO nanoparticles and SiO2/SC is adjusted by altering the thickness of the carbon layer. The X-ray photoelectron spectroscopy shows that owing to the strong electron-attracting ability SiO2 core contributes to leading the Pd0 active site in an electron-deficient state. The thickness of the carbon layer controls the ratio of Pd0/PdO, which enhances the anti-poisoning ability of the catalyst. Owing to the electron-deficient state of Pd0 and optimal ratio of Pd0/PdO, the hydrogen desorption rate of FAD on Pd is enhanced, and the turn over frequency of Pd/SiO2@SC-1:3 catalyst reaches 1138 h-1, which is ten times higher than that of the pristine Pd/SC catalyst. These results are believed to guide the design and development of highly active Pd-based catalysts for hydrogen generation via FAD.

Nanostructure Engineering and Electronic Modulation of a PtNi Alloy Catalyst for Enhanced Oxygen Reduction Electrocatalysis in Zinc-Air Batteries.

PtNi nanoalloys have demonstrated electrocatalysis superior to that of benchmark Pt/C catalysts for the oxygen reduction reaction (ORR), yet the underlying mechanisms remain underexplored. Herein, a PtNi/NC catalyst comprising PtNi nanoparticles (∼5.2 nm in size) dispersed on N-doped carbon frameworks was prepared using a simple pyrolysis strategy. Benefiting from the individual components and a hierarchical structure, the PtNi/NC catalyst exhibited outstanding ORR activity and stability (E1/2 = 0.82 V vs RHE and 8 mV negative shift after 20000 cycles), outperforming a commercial 20 wt % Pt/C catalyst (E1/2 = 0.81 V and 32 mV negative shift). A prototype zinc-air battery constructed using PtNi/NC as the air electrode catalyst achieved highly enhanced electrochemical performance, outperforming a battery constructed using Pt/C as the ORR catalyst. Density functional theory calculations revealed that the improved ORR activity of the PtNi nanoalloys originated from charge redistribution with a suitable metal d-band center to promote the formation of the ORR intermediates.

Experimental and Theoretical Insights into Enhanced Hydrogen Evolution over PtCo Nanoalloys Anchored on a Nitrogen-Doped Carbon Matrix.

The identification of synergistic effect of Pt-based alloys on hydrogen evolution reaction (HER) requires a combination of experimental studies and theoretical calculations. Here, we present the construction of uniform PtCo nanoparticles grown on N-doped carbon frameworks via pyrolyzing Pt and Co ions adsorbed polyaniline, whereby the nanostructure of the nanoalloys can be effectively tuned by controlling the calcination temperature. As-prepared PtCo@NC-900 shows the optimal HER performance in 0.5 M H2SO4, resulting in a high mass activity of 4.31 A mgPt-1 and excellent operation durability, which far exceeds that of commercial 20 wt % Pt/C (0.30 A mgPt-1). Density functional theory calculations further reveal that the improved HER activity on PtCo(111) is originated from the strong electronic interaction between Pt and Co with favorable electron transfer, allowing for a more suitable binding strength for hydrogen (i.e., ΔG*H = -0.164 eV) compared with that of pristine Pt(111) (-0.287 eV).

Benefits of Affective Pedagogical Agents in Multimedia Instruction.

The goal of the present study is to explore whether the affective states (happy or neutral) of a pedagogical agent (PA) in an online multimedia lesson yields different learning processes and outcomes, and whether the effects of affective PAs depend on the learners' emotion regulation strategies and their prior knowledge. In three experiments, undergraduates were asked to view a narrated animation about synaptic transmission that included either a happy PA (smiling expression and enthusiastic voice) or a neutral PA (neutral expression and calm voice) and subsequently took emotions, motivation, cognitive outcomes tests. Across three experiments, the happy PA group reported more positive emotions (ds = 0.70, 0.46, and 0.60) and higher level of motivation (ds = 0.76, 0.49, and 0.51) than the neutral PA group. Moreover, the happy PA prompted higher germane load (d = 0.41) than a neutral PA in Experiment 3. However, adding a happy PA to the screen did not improve learning performance. In addition, in Experiment 2, learners' usage of emotion regulation strategies moderated the effectiveness of affective PA on positive emotions in learners. Specifically, happy PAs increased the positive emotions of students who used expressive suppression strategy (d = 0.99) but not those who used cognitive reappraisal strategy (d = 0.13). In Experiment 3, the effectiveness of affective PAs was not moderated by learners' prior knowledge. Results support the cognitive affective theory of learning with media (CATLM) that students are happier and more motivated when they learn from happy PAs than from neutral PAs.

Hyperhomocysteinemia predicts renal function decline: a prospective study in hypertensive adults.

Hyper-homocysteinemia (HHcy) is associated with microalbuminuria and glomerular injury in general and diabetic populations. However, HHcy's role in hypertensive patients was not studied. We investigated whether HHcy is an independent risk factor for renal function decline and development of chronic kidney disease (CKD) in hypertensive men and women. This was a community-based prospective cohort study of 2,387 hypertensive adults without CKD at baseline, with a mean follow-up of 4.4 years. Baseline and follow-up levels of plasma Hcy, folate, vitamin B12, blood pressure and other pertinent covariables were obtained. CKD was defined as an estimated glomerular filtration rate (eGFR) <60 ml/min/per 1.73 m(2) and an eGFR decline rate >1 ml/min/per 1.73 m(2)/year. There was a graded association between Hcy tertiles and eGFR decline. Subjects in the 3(rd) tertile of Hcy levels had an accelerated rate of eGFR decline and an increased risk of incident CKD, as compared with those in the 1st tertile, after adjusting for age, gender, baseline diabetes, SBP, BMI, smoking, dyslipidemia, eGFR, folate and vitamin B12 levels. In conclusion, in this prospective cohort of Chinese hypertensive adults, elevated baseline plasma Hcy can serve as an independent biomarker to predict renal function decline and incident CKD.