A combinatorial descriptor for volcano relationships of electrochemical nitrogen reduction reaction

Though touted as a potential way to realize clean ammonia synthesis,electrochemical ammonia synthesis is currently limited by its catalytic efficiency.Great effort has been made to find catalysts with improved activity toward electrochemical nitrogen reduction reaction(eNRR).Rational screening of catalysts can be facilitated using the volcano relationship between catalytic activity and adsorption energy of an intermediate,namely,the activity descriptor.In this work,we proposeΔG^(*)_(NH_(2))+ΔG^(*)_(NNH)as a combinatorial descriptor,which shows better predictive power than traditional descriptors using the adsorption free energies of single intermediates.The volcano plots based on the combinatorial descriptor exhibits peak activity fixedly at the descriptor value corresponding to the formation free energy of NH3,regardless of the catalyst types;while the descriptor values correspond to the top activities for eNRR on volcano plots based on single descriptors usually vary with the types of catalysts.

Understanding the sluggish and highly variable transport kinetics of lithium ions in LiFePO_4

LiFePO_(4),one of the mainstream cathode materials of current EV batteries,exhibits experimental diffusion coefficients(D_(c))of Li^(+)which are not only several orders of magnitude lower than those predicted by the ionic hopping barriers obtained from theoretical calculations and spectroscopic measurements,but also span several orders from 10^(-14)to 10^(-18)cm^(2)s^(-1)under different states of charge(SOC)and the charging rates(C-rates).Atomic level understanding of such sluggishness and diversity of Li^(+)transport kinetics would be of significance in improving the rate performance of LiFePO_(4)through material and operation optimization but remain challenging.Herein,we show that the high sensitivity of Li^(+)hopping barriers on the local Li–Li coordination environments(numbers and configurations)plays a key role in the ion transport kinetics.This is due a neural network-based deep potential(DP)which allows accurate and efficient calculation of hopping barriers of Li^(+)in LiFePO_(4)with various Li–Li coordination environments,with which the kinetic Monte-Carlo(KMC)method was employed to determine the D_(c)values at various C-rates and SOC across a broad spectrum.Especially,an accelerated KMC simulation strategy is proposed to obtain the D_(c)values under a wide range of SOC at low C-rates,which agree well with that obtained from the galvanostatic intermittent titration technique(GITT).The present study provides accurate descriptions of Li^(+)transport kinetics at both very high and low C-rates,which remains challenging to experiments and first-principles calculations,respectively.Finally,it is revealed that the gradient distributions of Li^(+)density along the diffusion path result in great asymmetry in the barriers of the forward and backward hopping,causing very slow diffusion of Li^(+)and the diverse variation of D_(c).

Discrepant roles of adsorbed OH^* species on IrWOx for boosting alkaline hydrogen electrocatalysis

Improving the slow kinetics of alkaline hydrogen electrode reactions, involving hydrogen oxidation and evolution reactions(HOR/HER) is highly desirable for accelerating the commercialization of alkaline exchange membrane-based fuel cells(AEMFCs) and water electrolyzers(AEMWEs). However, fundamental understanding of the mechanism for HOR/HER catalysis under alkaline media is still debatable. Here we develop an amorphous tungsten oxide clusters modified iridium-tungsten nanocrystallines(Ir WOx)which exhibited by far the highest exchange current density and mass activity, about three times higher than the commercial Pt/C toward alkaline HOR/HER. Density functional theory(DFT) calculations reveal the WOxclusters act as a pivotal role to boost reversible hydrogen electrode reactions in alkaline condition but via different mechanisms, which are, hydrogen binding energy(HBE) mechanism for HOR and bifunctional mechanism for HER. This work is expected to promote our fundamental understanding about the alkaline HOR/HER catalysis and provide a new avenue for rational design of highly efficient electrocatalysts toward HOR/HER under alkaline electrolytes.

A potential-driven switch of activity promotion mode for the oxygen evolution reaction at Co_(3)O_(4)/NiO_(x)H_(y) interface

Co_(3)O_(4)spinel oxides have manifested promising activity toward the oxygen evolution reaction(OER)through effective modifications.For them to become top electrocatalysts,however,accurate accounts of the catalytic kinetics are essential to gain a deep understanding of the activity promotion mechanisms.Herein,we use a newly proposed kinetic model based on energetic span as the rate-determining term for the electrocatalytic reaction to throw light on the promotion mechanism of Co_(3)O_(4)interfaced with nickel hydroxides(NiO_(x)H_(y))for the OER.We find that depending on the electrode potential,the OER kinetics at the designed interface between Co_(3)O_(4)and NiO_(x)H_(y)are boosted in entirely different ways.As a result,the OER can occur at a lower onset potential as well as a low Tafel slope.This work emphasizes the benefit of using rational theoretical models for electrocatalyst design.