Carbon–carbon bond cleavage reactions, adapted to deconstruct aliphatic hydrocarbon polymers and recover the intrinsic energy and carbon value in plastic waste, have typically been catalysed by metal nanoparticles or air-sensitive organometallics. Metal oxides that serve as supports for these catalysts are typically considered to be inert. Here we show that Earth-abundant, non-reducible zirconia catalyses the hydrogenolysis of polyolefins with activity rivalling that of precious metal nanoparticles. To harness this unusual reactivity, our catalytic architecture localizes ultrasmall amorphous zirconia nanoparticles between two fused platelets of mesoporous silica. Macromolecules translocate from bulk through radial mesopores to the highly active zirconia particles, where the chains undergo selective hydrogenolytic cleavage into a narrow, C18-centred distribution. Calculations indicated that C–H bond heterolysis across a Zr–O bond of a Zr(O)2 adatom model for unsaturated surface sites gives a zirconium hydrocarbyl, which cleaves a C–C bond via β-alkyl elimination.

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Disorder induced phase slip (PS) events appearing in the current voltage characteristics (IVCs) are reported for two-dimensional TiN thin films produced by a robust substrate mediated nitridation technique. Here, high temperature annealing of Ti/Si3N4 based metal/substrate assembly is the key to produce majority phase TiN accompanied by TiSi2 & elemental Si as minority phases. The method itself introduces different level of disorder intrinsically by tuning the amount of the non-superconducting minority phases that are controlled by annealing temperature (Ta) and the film thickness. The superconducting critical temperature (Tc) strongly depends on Ta and the maximum Tc obtained from the demonstrated technique is about 4.8 K for the thickness range ~ 12 nm and above. Besides, the dynamics of IVCs get modulated by the appearance of intermediated resistive steps for decreased Ta and the steps get more prominent for reduced thickness. Further, the deviation in the temperature dependent critical current (Ic) from the Ginzburg–Landau theoretical limit varies strongly with the thickness. Finally, the Tc, intermediate resistive steps in the IVCs and the depairing current are observed to alter in a similar fashion with Ta and the thickness indicating the robustness of the synthesis process to fabricate disordered nitride-based superconductor.

In 2D disordered superconductors prior to superconducting transition, the appearance of a resistance peak in the temperature dependent resistance [R(T)] measurements indicates the presence of weak localization (WL) & electron-electron interaction (EEI) in diffusion channel and superconducting fluctuations in the Cooper channel. Here, we demonstrate an interplay between superconducting fluctuations and electronelectron interaction by low temperature magnetotransport measurements for a set of 2D disordered TiN thin films. While cooling down the sample, a characteristic temperature T* is obtained from the R(T) at which superconducting fluctuations start to appear. The upturn in R(T) above T* corresponds to WL and/or EEI. By the temperature and field dependences of the observed resistance, we show that the upturn in R(T) originates mainly from EEI with a negligible contribution from WL. Further, we have used the modified Larkin's electron-electron attraction strength β(T/Tc), containing a field induced pair breaking parameter, in the Maki-Thompson (MT) superconducting fluctuation term. Here, the temperature dependence of the β(T/Tc) obtained from the magnetoresistance analysis shows a diverging behavior close to Tc and it remains almost constant at higher temperature within the limit of ln(T/Tc) <1. Interestingly, the variation of β(T/Tc) on the reduced temperature (T/Tc) offers a common trend which has been closely followed by all the concerned samples presented in this study. Finally, the temperature dependence of inverse phase scattering time (𝜏 𝜙 −1 ), as obtained from the magnetoresistance analysis, clearly shows two different regimes; the first one close to Tc follows the Ginzburg-Landau relaxation rate (𝜏 𝐺𝐿 −1 ), whereas, the second one at high temperature varies almost linearly with temperature indicating the dominance of inelastic electron-electron scattering for the dephasing mechanism. These two regimes are followed in a generic way by all the samples in spite of being grown under different growth conditions.