Understanding Catalytic Activity Trends in the Oxygen Reduction Reaction.

Despite the dedicated search for novel catalysts for fuel cell applications, the intrinsic oxygen reduction reaction (ORR) activity of materials has not improved significantly over the past decade. Here, we review the role of theory in understanding the ORR mechanism and highlight the descriptor-based approaches that have been used to identify catalysts with increased activity. Specifically, by showing that the performance of the commonly studied materials (e.g., metals, alloys, carbons, etc.) is limited by unfavorable scaling relationships (for binding energies of reaction intermediates), we present a number of alternative strategies that may lead to the design and discovery of more promising materials for ORR.

Efficient Pourbaix diagrams of many-element compounds.

Pourbaix diagrams have been used extensively to evaluate stability regions of materials subject to varying potential and pH conditions in aqueous environments. However, both recent advances in high-throughput material exploration and increasing complexity of materials of interest for electrochemical applications pose challenges for performing Pourbaix analysis on multidimensional systems. Specifically, current Pourbaix construction algorithms incur significant computational costs for systems consisting of four or more elemental components. Herein, we propose an alternative Pourbaix construction method that filters all potential combinations of species in a system to only those present on a compositional convex hull. By including axes representing the quantities of H+ and e- required to form a given phase, one can ensure every stable phase mixture is included in the Pourbaix diagram and reduce the computational time required to construct the resultant Pourbaix diagram by several orders of magnitude. This new Pourbaix algorithm has been incorporated into the pymatgen code and the Materials Project website, and it extends the ability to evaluate the Pourbaix stability of complex multicomponent systems.

Resin-modified glass ionomer cement vs composite for orthodontic bonding: A multicenter, single-blind, randomized controlled trial.

INTRODUCTION: In this study, we aimed to compare the incidence of new demineralized lesions and bond failures between 2 groups of participants wearing fixed orthodontic appliances bonded with either light-cured resin-modified glass ionomer cement or light-cured composite. METHODS: This trial was a multicenter (6 centers: 2 teaching hospitals, 4 specialist orthodontic practices), single-blinded, randomized controlled trial with 2 parallel groups. Patients aged 11 years or older, in the permanent dentition, and about to start fixed orthodontic treatment in these 6 centers were randomly allocated to have either resin-modified glass ionomer cement or light-cured composite for bonding brackets, forward of the first molars. Pretreatment and day-of-debond digital photographic images were taken of the teeth and assessed by up to 5 clinical and 3 lay assessors for the presence or absence of new demineralized lesions and the esthetic impact. The assessors were masked as to group allocation. RESULTS: We randomized 210 participants, and 197 completed the trial. There were 173 with complete before-and after-digital images of the teeth. The incidence of new demineralized lesions was 24%; but when the esthetic impact was taken into account, this was considerably lower (9%). There was no statistically significant difference between the bracket adhesives in the numbers with at least 1 new demineralized lesion (risk ratio,1.25; 95% confidence interval, 0.74-2.13; P = 0.403) or first-time bracket failure (risk ratio,0.88; 95% confidence interval, 0.67-1.16; P = 0.35). There were no adverse effects. CONCLUSIONS: There is no evidence that the use of resin modified glass ionomer cement over light-cured composite for bonding brackets reduces the incidence of new demineralized lesions or bond failures. There might be other reasons for using resin modified glass ionomer cement. REGISTRATION: This trial was registered at ClinicalTrials.govNCT01925924. PROTOCOL: The protocol is available from the corresponding author on request.

Force-Based Method to Determine the Potential Dependence in Electrochemical Barriers.

Determining ab initio potential-dependent energetics is critical to the investigation of mechanisms for electrochemical reactions. While methodology for evaluating reaction thermodynamics is established, simulation techniques for the corresponding kinetics is still a major challenge owing to a lack of potential control, finite cell size effects, or computational expense. In this work, we develop a model that allows for computing electrochemical activation energies from just a handful of density functional theory (DFT) calculations. The sole input into the model are the atom-centered forces obtained from DFT calculations performed on a homogeneous grid composed of varying field strengths. We show that the activation energies as a function of the potential obtained from our model are consistent for different supercell sizes and proton concentrations for a range of electrochemical reactions.

Generalizable Trends in Electrochemical Protonation Barriers.

Predicting activation energies for reaction steps is essential for modeling catalytic processes, but accurate barrier simulations often require considerable computational expense, especially for electrochemical reactions. Given the challenges of barrier computations and the growing promise of electrochemical routes for various processes, generalizable energetic trends in electrochemistry can significantly aid in analyzing reaction networks and building microkinetic models. Herein, we employ density functional theory and machine learning nudged elastic band models to simulate electrochemical protonation of *C, *N, and *O monatomic adsorbates from hydronium on a series of transition metal surfaces. We observe a consistent trend of decreasing protonation reaction energies yet increasing activation barriers from *O to *N to *C. Analysis of bond orders and reaction pathways provides insight into the origin of the observed trends in protonation energetics. We hypothesize that these results are relevant for polyatomic adsorbates, which can simplify analysis of reaction mechanisms and inform catalyst design.

Circumventing Scaling Relations in Oxygen Electrochemistry Using Metal-Organic Frameworks.

It has been well-established that unfavorable scaling relationships between *OOH, *OH, and *O are responsible for the high overpotentials associated with oxygen electrochemistry. A number of strategies have been proposed for breaking these linear constraints for traditional electrocatalysts (e.g., metals, alloys, metal-doped carbons); such approaches have not yet been validated experimentally for heterogeneous catalysts. Development of a new class of catalysts capable of circumventing such scaling relations remains an ongoing challenge in the field. In this work, we use density functional theory (DFT) calculations to demonstrate that bimetallic porphyrin-based MOFs (PMOFs) are an ideal materials platform for rationally designing the 3-D active site environments for oxygen reduction reaction (ORR). Specifically, we show that the *OOH binding energy and the theoretical limiting potential can be optimized by appropriately tuning the transition metal active site, the oxophilic spectator, and the MOF topology. Our calculations predict theoretical limiting potentials as high as 1.07 V for Fe/Cr-PMOF-Al, which exceeds the Pt/C benchmark for 4e ORR. More broadly, by highlighting their unique characteristics, this work aims to establish bimetallic porphyrin-based MOFs as a viable materials platform for future experimental and theoretical ORR studies.

Medical disorders and orthodontics.

The orthodontic treatment of patients with medical disorders is becoming an increasing aspect of modern day practice. This article will draw attention to some of the difficulties faced when orthodontic treatment is provided and will make recommendations on how to avoid potential problems.