Moving Mountains: Reshaping the Activity Volcano of Electrocatalysis with Fluxional Subnano Clusters

The activity volcano derived from Sabatier analysis provides intuitive guide for catalyst design, but it also imposes fundamental limitations on the maximal activity and the pool of high-performance elements. Here we show that the activity volcano for oxygen reduction reaction (ORR) can be shifted and reshaped in the subnano regime. The fluxional behavior of subnano clusters, in both isolated and graphite-supported forms, not only breaks the linear scaling relationships but also causes an overall strengthening in adsorbate binding. The metals with optimal adsorbate binding in the bulk form (Pt/Pd) thus suffer over-binding issues, while the metals that under-bind in the bulk form (Ag/Au) gain optimal reaction energetics. In addition, the potential-dependence of isomer energies differ, causing non-linear reaction free energy-potential relations and enabling population-tuning of specific isomers, thereby surpassing the apex of the activity volcano. The shift of the volcano that puts under-binding elements closer to the top is likely general in fluxional cluster catalysis, and can be used for cluster catalyst design.

Direct Metal-Free Transformation of Alkynes to Nitriles: Computational Evidence for the Precise Reaction Mechanism

Density functional theory calculations elucidated the precise reaction mechanism for the conversion of diphenylacetylenes into benzonitriles involving the cleavage of the triple C≡C bond, with N-iodosuccinimide (NIS) as an oxidant and trimethylsilyl azide (TMSN3) as a nitrogen donor. The reaction requires six steps with the activation barrier ΔG‡ = 33.5 kcal mol−1 and a highly exergonic reaction free-energy ΔGR = −191.9 kcal mol−1 in MeCN. Reaction profiles agree with several experimental observations, offering evidence for the formation of molecular I2, interpreting the necessity to increase the temperature to finalize the reaction, and revealing thermodynamic aspects allowing higher yields for alkynes with para-electron-donating groups. In addition, the proposed mechanism indicates usefulness of this concept for both internal and terminal alkynes, eliminates the option to replace NIS by its Cl- or Br-analogues, and strongly promotes NaN3 as an alternative to TMSN3. Lastly, our results advise increasing the solvent polarity as another route to advance this metal-free strategy towards more efficient processes.

Prediction of Alkanolamine pKa Values by Combined Molecular Dynamics Free Energy Simulations and ab initio Calculations

We use molecular dynamics free energy simulations in conjunction with quantum chemical calculations of gas phase reaction free energy to predict alkanolamines pka values. <br>

Prediction of Alkanolamine pKa Values by Combined Molecular Dynamics Free Energy Simulations and ab initio Calculations

We use molecular dynamics free energy simulations in conjunction with quantum chemical calculations of gas phase reaction free energy to predict alkanolamines pka values. <br>

Vacuum decomposition thermodynamics and experiments of recycled lead carbonate from waste lead acid battery

Lead acid batteries have been widely used in different fields, so abundant waste lead acid battery was generated. Waste lead acid battery is regarded as a toxic material due to the metallic lead and the lead paste compounds. Once lead and its compounds enter the human body and the environment, which will cause serious threats. At present, the waste lead acid batteries are mainly recovered in the form of metal lead, which has many problems. Thus, this paper put forward a novel technology to recycle waste lead acid battery. Vacuum thermal decomposition was employed to treat recycled lead carbonate from waste lead acid battery. Thermodynamics analysis and experiments were finished from the reaction free energy of lead carbonate decomposition and vacuum furnace. The results showed that the recycled lead carbonate began to be decomposed when the temperature reached 250?C. Above 340?C, most of intermediate PbCO3?2PbO were converted to red ?-PbO and then transformed to yellow ?-PbO when the temperature was raised further to 460?C. Furthermore, the study provided the fundamental data for the preparation of ?-PbO and ?-PbO in vacuum, which also demonstrated a new way for the reuse of spent lead acid battery resource and an outlook of sustainable production.

Beyond the classical thermodynamic contributions to hydrogen atom abstraction reactivity

Hydrogen atom abstraction (HAA) reactions are cornerstones of chemistry. Various (metallo)enzymes performing the HAA catalysis evolved in nature and inspired the rational development of multiple synthetic catalysts. Still, the factors determining their catalytic efficiency are not fully understood. Herein, we define the simple thermodynamic factor η by employing two thermodynamic cycles: one for an oxidant (catalyst), along with its reduced, protonated, and hydrogenated form; and one for the substrate, along with its oxidized, deprotonated, and dehydrogenated form. It is demonstrated that η reflects the propensity of the substrate and catalyst for (a)synchronicity in concerted H+/e− transfers. As such, it significantly contributes to the activation energies of the HAA reactions, in addition to a classical thermodynamic (Bell–Evans–Polanyi) effect. In an attempt to understand the physicochemical interpretation of η, we discovered an elegant link between η and reorganization energy λ from Marcus theory. We discovered computationally that for a homologous set of HAA reactions, λ reaches its maximum for the lowest |η|, which then corresponds to the most synchronous HAA mechanism. This immediately implies that among HAA processes with the same reaction free energy, ΔG0, the highest barrier (≡ΔG≠) is expected for the most synchronous proton-coupled electron (i.e., hydrogen) transfer. As proof of concept, redox and acidobasic properties of nonheme FeIVO complexes are correlated with activation free energies for HAA from C−H and O−H bonds. We believe that the reported findings may represent a powerful concept in designing new HAA catalysts.

Size effect of oxygen reduction reaction on nitrogen-doped graphene quantum dots

The adsorption strength of ORR intermediates, the reaction free energy of rate-determining step, and the overpotential increase with the increase of the size of N-doped graphene quantum dots.