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Electrocatalysis enables the industrial transition to sustainable production of chemicals using abundant precursors and electricity from renewable sources. De-centralized production of hydrogen peroxide (H2O2) from water and oxygen of air is highly desirable for daily life and industry. We report an effective electrochemical refinery (e-refinery) for H2O2 by means of electrocatalysis-controlled comproportionation reaction (2(H)O + O -> 2(HO)), feeding pure water and oxygen only. Mesoporous nickel (II) oxide (NiO) was used as electrocatalyst for oxygen evolution reaction (OER), producing oxygen at the anode. Conducting polymer poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) drove the oxygen reduction reaction (ORR), forming H2O2 on the cathode. The reactions were evaluated in both half-cell and device configurations. The performance of the H2O2 e-refinery, assembled on anion-exchange solid electrolyte and fed with pure water, was limited by the unbalanced ionic transport. Optimization of the operation conditions allowed a conversion efficiency of 80%. Funding: Swedish Agency for Innovation Systems (Vinnova) [2016-05156]; Swedish Energy Agency [42022-1]; Swedish Research Council [VR 2021-04427, VR 2019-05577, VR 2016-05990]; Centre in Nanoscience and Technology (CeNano, Linkoeping Institute of Technology (LiTH), Linkoeping University, 2020, 2021); Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoeping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; Knut and Alice Wallenberg Foundation (H2O2) [KAW 2018.0058]

A combined high-power impulse and dc magnetron co-sputtering (HiPIMS/DCMS) technique is used to deposit Ti0.6Al0.32Si0.08N films with 1-fold substrate table rotation. Layers are grown at two different substrate-target separations, two different rotational speeds, and with different values of substrate bias. The aim is to study the role of (1) overlap between ion and neutral fluxes generated from HiPIMS and DCMS sources, respectively, and (2) the subplantation range of low-mass ions. Results from X-ray diffractometry highlight the necessity of flux intermixing in the formation of the metastable B1-structured TiAlSiN solid solutions. All films grown at short target-to-substrate distance contain the hexagonal AlN phase, as there is essentially no overlap between HiPIMS and DCMS fluxes, thus the Al+ and Si+ subplantation is very limited. Under conditions of high flux intermixing corresponding to larger target-to-substrate distance, no w-AlN forms irrespective of rotational speed (1 or 3 rpm) and bias amplitude (120 or 480 V), indicating that the role of Al+/Si+ and Ti flux overlap is crucial for the phase formation during film growth by HiPIMS/DCMS with substrate rotation. This conclusion is further supported by the fact that the reduction of the bilayer thickness with increasing the target-to-substrate distance (hence increasing flux overlap) is larger for films grown with higher amplitude of the substrate bias, indicative of more efficient Al+/Si+ subplantation into the c-TiN phase. Single-phase films with the hardness close to that of layers grown with stationary substrate table can be achieved, however, at the expense of higher compressive stress. Funding: VINNOVA (FunMat-II project) [2016-05156]; Swedish Research Council [2017-03813, 2017-06701]; Swedish government strategic research area grant AFM - SFO MatLiU [2009-00971]