Doping Effects on the Performance of Paired Metal Catalysts for the Hydrogen Evolution Reaction

Metal heteroatoms dispersed in nitrogen-doped graphene display promising catalytic activity for fuel cell reactions such as the hydrogen evolution reaction (HER). Here we explore the effects of dopant concentration on the synergistic catalytic behaviour of a paired metal atom active site comprised of Co and Pt atoms. The metals are coordinated to six atoms in a vacancy of N-doped graphene. We find that HER activity is enhanced with increasing N concentration, where the free energy of hydrogen atom adsorption ranges from 0.23 to -0.42 eV as the doping changes from a single N atom doped in the pore, to fully doped coordination sites. The results indicated that the effect of N is to make the Co atom more active towards H adsorption and presents a means through which transition metals can be modified to make more effective and sustainable fuel cell catalysts

Evaluating the catalytic efficiency of paired, single-atom catalysts for the oxygen reduction reaction

Paired, single-atom catalysts have been shown to demonstrate synergistic effects computationally and experimentally which enable them to outperform the benchmark catalyst, Pt/C, for electrochemical reactions. We explore the limit of these catalysts by screening different transition metal atoms (M = Co, Pt, Fe, Ni) in nitrogen-doped graphene for their ability to catalyze the oxygen reduction reaction (ORR). We employ density functional theory methods to explore the electronic factors affecting catalytic activity in an effort to rationalize trends in the performance of materials which are promising candidates for the next generation of electrocatalysts. It is found that CoPt@N8V4, composed of paired Co and Pt in a nitrogen-doped four-atom vacancy in graphene (N8V4), performs ideally for the ORR with an overpotential (η) of 0.30 V, followed closely by Co and Ni (η = 0.35 V) and paired Co (η = 0.37 V). The origin of activity is suggested to be the changing reduction potential of the active Co atom via the local distortion of the pore by the spectating metal partner. We utilize the ORR scaling relations and plot catalytic activity on a volcano plot, which we correlate with the degree of antibonding interactions with the O atom in the OH intermediate of the ORR. We establish that the local tuning of paired catalysts allows for the reactivity of metal atoms to be specifically modified for desirable reactivity

Critical amplitudes and mass spectrum of the 2D Ising model in a magnetic field

We compute the spectrum and several critical amplitudes of the two dimensional Ising model in a magnetic field with the transfer matrix method. The three lightest masses and their overlaps with the spin and the energy operators are computed on lattices of a width up to L=21. In extracting the continuum results we also take into account the corrections to scaling due to irrelevant operators. In contrast with previous Monte Carlo simulations our final results are in perfect agreement with the predictions of S-matrix and conformal field theory. We also obtain the amplitudes of some of the subleading corrections, for which no S-matrix prediction has yet been obtained.Comment: Final version, minor changes in the text, 52 page

State-to-state reaction probabilities for the H+O(2)(v,j) -> O+OH(v',j') reaction on three potential energy surfaces

We report state-to-state and total reaction probabilities for J=0 and total reaction probabilities for J=2 and 4 for the title reaction, both for ground-state and initially rovibrationally excited reactants. The results for three different potential energy surfaces are compared and contrasted. The potential energy surfaces employed are the DMBE IV surface by Pastrana [J. Phys. Chem. 94, 8073 (1990)], the surface by Troe and Ushakov (TU) [J. Chem. Phys. 115, 3621 (2001)], and the new XXZLG ab initio surface by Xu [J. Chem. Phys. 122, 244305 (2005)]. Our results show that the total reaction probabilities from both the TU and XXZLG surfaces are much smaller in magnitude for collision energies above 1.2 eV compared to the DMBE IV surface. The three surfaces also show different behavior with regards to the effect of initial state excitation. The reactivity is increased on the XXZLG and the TU surfaces and decreased on the DMBE IV surface. Vibrational and rotational product state distributions for the XXZLG and the DMBE IV surface show different behaviors for both types of distributions. Our results show that for energies above 1.25 eV the dynamics on the DMBE IV surface are not statistical. However, there is also evidence that the dynamics on the XXZLG surface are not purely statistical for energies above the onset of the first excited product vibrational state v'=1. The magnitude of the total reaction probability is decreased for J>0 for the DMBE IV and the XXZLG surfaces for ground-state reactants. However, for initially rovibrationally excited reactants, the total reaction probability does not decrease as expected for both surfaces. As a result the total cross section averaged over all Boltzmann accessible rotational states may well be larger than the cross section reported in the literature for j=1. (C) 2007 American Institute of Physics

Enriching the hydrogen storage capacity of carbon nanotube doped with polylithiated molecules

In a quest to find optimum materials for efficient storage of clean energy, we have performed first principles calculations to study the structural and energy storage properties of one-dimensional carbon nanotubes (CNTs) functionalized with polylithiated molecules (PLMs). Van der Waals corrected calculations disclosed that various PLMs like CLi, CLi, CLi, OLi, OLi, OLi, bind strongly to CNTs even at high doping concentrations ensuring a uniform distribution of dopants without forming clusters. Bader charge analysis reveals that each Li in all the PLMs attains a partial positive charge and transform into Li cations. This situation allows multiple H molecules adsorbed with each Li through the polarization of incident H molecules via electrostatic and van der Waals type of interaction. With a maximum doping concentration, that is 3CLi/3CLi and 3OLi/3OLi a maximum of 36 H molecules could be adsorbed that corresponds to a reasonably high H storage capacity with the adsorption energies in the range of −0.33 to −0.15 eV/H. This suits the ambient condition applications

Study of the H+O2 reaction by means of quantum mechanical and statistical approaches: The dynamics on two different potential energy surfaces

The possible existence of a complex-forming pathway for the H+O2 reaction has been investigated by means of both quantum mechanical and statistical techniques. Reaction probabilities, integral cross sections, and differential cross sections have been obtained with a statistical quantum method and the mean potential phase space theory. The statistical predictions are compared to exact results calculated by means of time dependent wave packet methods and a previously reported time independent exact quantum mechanical approach using the double many-body expansion (DMBE IV) potential energy surface (PES) [Pastrana et al., J. Phys. Chem. 94, 8073 (1990)] and the recently developed surface (denoted XXZLG) by Xu et al. [J. Chem. Phys. 122, 244305 (2005)]. The statistical approaches are found to reproduce only some of the exact total reaction probabilities for low total angular momenta obtained with the DMBE IV PES and some of the cross sections calculated at energy values close to the reaction threshold for the XXZLG surface. Serious discrepancies with the exact integral cross sections at higher energy put into question the possible statistical nature of the title reaction. However, at a collision energy of 1.6 eV, statistical rotationally resolved cross sections managed to reproduce the experimental cross sections for the H+O2(v=0,j=1)-->OH(v[prime]=1,j[prime])+O process reasonably well. ©2008 American Institute of Physic

Error bounds for the large-argument asymptotic expansions of the Hankel and Bessel functions

In this paper, we reconsider the large-argument asymptotic expansions of the Hankel, Bessel and modified Bessel functions and their derivatives. New integral representations for the remainder terms of these asymptotic expansions are found and used to obtain sharp and realistic error bounds. We also give re-expansions for these remainder terms and provide their error estimates. A detailed discussion on the sharpness of our error bounds and their relation to other results in the literature is given. The techniques used in this paper should also generalize to asymptotic expansions which arise from an application of the method of steepest descents.Comment: 32 pages, 2 figures, accepted for publication in Acta Applicandae Mathematica

Carbon nitrides: synthesis and characterization of a new class of functional materials

Carbon nitride compounds with high N[thin space (1/6-em)]:[thin space (1/6-em)]C ratios and graphitic to polymeric structures are being investigated as potential next-generation materials for incorporation in devices for energy conversion and storage as well as for optoelectronic and catalysis applications. The materials are built from C- and N-containing heterocycles with heptazine or triazine rings linked via sp2-bonded N atoms (N(C)3 units) or –NH– groups. The electronic, chemical and optical functionalities are determined by the nature of the local to extended structures as well as the chemical composition of the materials. Because of their typically amorphous to nanocrystalline nature and variable composition, significant challenges remain to fully assess and calibrate the structure–functionality relationships among carbon nitride materials. It is also important to devise a useful and consistent approach to naming the different classes of carbon nitride compounds that accurately describes their chemical and structural characteristics related to their functional performance. Here we evaluate the current state of understanding to highlight key issues in these areas and point out new directions in their development as advanced technological materials.Our work on carbon nitride materials has been supported by the EPSRC (EP/L017091/1) and the EU Graphene Flagship grant agreement No. 696656 - GrapheneCore1. Additional support to advance the science and technology of these materials was also received from the UCL Enterprise Fund and the Materials Innovation Impact Acceleration funding enabled by the UK EPSRC

Coriolis coupling effects in the dynamics of deep well reactions: Application to the H+ + D2 reaction

We present exact and estimated quantum differential and integral cross sections as well as product state distributions for the title reaction. We employ a time-dependent wavepacket method including all Coriolis couplings and also an adapted code where the helicity quantum number and with this the Coriolis couplings have been truncated. Results from helicity truncated as well as helicity conserving (HC) calculation are presented. The HC calculations fail to reproduce the exact results due to the influence of the centrifugal barrier. While the truncated calculation overestimate the exact integral cross sections they reproduce the features of the integral cross section very well. We also find that the product rotational state distributions are well reproduced if the maximum helicity state is chosen carefully. The helicity truncated calculations fail to give a good approximation of differential cross sections