An on-line application for ΔR calculation

A regional offset (ΔR) from the marine radiocarbon calibration curve is widely used in calibration software (eg CALIB, OxCal) but often is not calculated correctly. While relatively straightforward for known age samples, such as mollusks from museum collections or banded corals, it is more difficult to calculate ΔR and the uncertainty in ΔR for 14C dates on paired marine and terrestrial samples. Previous researchers have often utilized classical intercept methods (Reimer et al. 2002; Dewar et al. 2012, Russell et al. 2011) but this does not account for the full calibrated probability density function (PDF). We have developed an on-line application for performing these calculations for known age, paired marine and terrestrial 14C dates, or U-Th dated corals which is available at http://calib.qub.ac.uk/deltar

Catalyst screening: Refinement of the origin of the volcano curve and its implication in heterogeneous catalysis

Understanding the overall catalytic activity trend for rational catalyst design is one of the core goals in heterogeneous catalysis. In the past two decades, the development of density functional theory (DFT) and surface kinetics make it feasible to theoretically evaluate and predict the catalytic activity variation of catalysts within a descriptor-based framework. Thereinto, the concept of the volcano curve, which reveals the general activity trend, usually constitutes the basic foundation of catalyst screening. However, although it is a widely accepted concept in heterogeneous catalysis, its origin lacks a clear physical picture and definite interpretation. Herein, starting with a brief review of the development of the catalyst screening framework, we use a two-step kinetic model to refine and clarify the origin of the volcano curve with a full analytical analysis by integrating the surface kinetics and the results of first-principles calculations. It is mathematically demonstrated that the volcano curve is an essential property in catalysis, which results from the self-poisoning effect accompanying the catalytic adsorption process. Specifically, when adsorption is strong, it is the rapid decrease of surface free sites rather than the augmentation of energy barriers that inhibits the overall reaction rate and results in the volcano curve. Some interesting points and implications in assisting catalyst screening are also discussed based on the kinetic derivation. Moreover, recent applications of the volcano curve for catalyst design in two important photoelectrocatalytic processes (the hydrogen evolution reaction and dye-sensitized solar cells) are also briefly discussed.