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This work presents a detailed investigation aimed at understanding the key mechanisms governing nitric oxide (NO) production in N 2 -O 2 discharges by systematically comparing experimental results to modeling data. The experimental phase capitalizes on radiofrequency (13.56 MHz) discharges, sustained at 5 mbar pressure conditions, featuring varying concentrations of oxygen, ranging from pure N 2 plasma to air-like mixtures. On the modeling front, we adopt an integrated approach that combines the solution of the Boltzmann equation for electrons with a system of rate balance equations for heavy species. To account for ground state NO(X) generation at the reactor wall, we combine the volume chemistry with a mesoscopic description of the surface, taking into account adsorption sites and various elementary surface phenomena. Comparisons between experiments and modeling demonstrate very good agreement, extending beyond NO(X) formation to encompass other species in the plasma such as N 2 O(X) and atomic nitrogen N( 4 S). Noteworthy findings include (i) the pivotal role of surface mechanisms in NO(X) production, particularly at low oxygen content values; (ii) the significance of accurately describing the postdischarge phase, where depletion of plasma species occurs at different time scales (millisecond range); and (iii) the importance of vibrationally and electronically excited states (e.g., O 2 (b)) in elucidating NO(X) formation dynamics, crucial for unraveling reaction pathways and energy transfer processes. This work makes an important step toward formulating a comprehensive reaction mechanism for N 2 and N 2 -O 2 plasmas applied to nitrogen fixation, covering both volume and surface mechanisms, and lays a robust foundation for future research on plasma-based NO(X) production, particularly in the presence of catalysts.

Nickel cobalt oxides (NCOs) are promising, non-precious oxygen evolution reaction (OER) electrocatalysts. However, the stoichiometry-dependent electrochemical behavior makes it crucial to understand the structure-OER relationship. In this work, NCO thin film model systems are prepared using atomic layer deposition. In-depth film characterization shows the phase transition from Ni-rich rock-salt films to Co-rich spinel films. Electrochemical analysis in 1 m KOH reveals a synergistic effect between Co and Ni with optimal performance for the 30 at.% Co film after 500 CV cycles. Electrochemical activation correlates with film composition, specifically increasing activation is observed for more Ni-rich films as its bulk transitions to the active (oxy)hydroxide phase. In parallel to this transition, the electrochemical surface area (ECSA) increases up to a factor 8. Using an original approach, the changes in ECSA are decoupled from intrinsic OER activity, leading to the conclusion that 70 at.% Co spinel phase NCO films are intrinsically the most active. The studies point to a chemical composition dependent OER mechanism: Co-rich spinel films show instantly high activities, while the more sustainable Ni-rich rock-salt films require extended activation to increase the ECSA and OER performance. The results highlight the added value of working with model systems to disclose structure-performance mechanisms., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Alkaline water electrolysis is a sustainable way to produce green hydrogen using renewable electricity. Even though the rates of the cathodic hydrogen evolution reaction (HER) are 2-3 orders of magnitude less under alkaline conditions than under acidic conditions, the possibility of using non-precious metal catalysts makes alkaline HER appealing. We identify a novel and facile route for substantially improving HER performance via the use of commercially available NiTi shape memory alloys, which upon heating undergo a phase transformation from the monoclinic martensite to the cubic austenite structure. While the room-temperature performance is modest, austenitic NiTi outperforms Pt (which is the state-of-the-art HER electrocatalyst) in terms of current density by ≤50% at 80 °C. Surface ensembles presented by the austenite phase are computed with density functional theory to bind hydrogen more weakly than either metallic Ni or Ti and to have binding energies ideally suited for HER.

Commercialization of photoelectrochemical (PEC) water-splitting devices requires the development of large-area, low-cost photoanodes with high efficiency and photostability. Herein, we address these challenges by using scalable fabrication techniques and porous transport layer (PTLs) electrode supports. We demonstrate the deposition of W-doped BiVO 4 on Ti PTLs using successive-ionic-layer-adsorption-and-reaction methods followed by boron treatment and chemical bath deposition of NiFeOOH co-catalyst. The use of PTLs that facilitate efficient mass and charge transfer allowed the scaling of the photoanodes (100 cm 2 ) while maintaining ~90 % of the performance obtained with 1 cm 2 photoanodes for oxygen evolution reaction, that is, 2.10 mA cm -2 at 1.23 V vs. RHE. This is the highest reported performance to date. Integration with a polycrystalline Si PV cell leads to bias-free water splitting with a stable photocurrent of 208 mA for 6 h and 2.2 % solar-to-hydrogen efficiency. Our findings highlight the importance of photoelectrode design towards scalable PEC device development., (© 2023 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

NiO-based electrocatalysts, known for their high activity, stability, and low cost in alkaline media, are recognized as promising candidates for the oxygen evolution reaction (OER). In parallel, atomic layer deposition (ALD) is actively researched for its ability to provide precise control over the synthesis of ultrathin electrocatalytic films, including film thickness, conformality, and chemical composition. This study examines how NiO bulk and surface properties affect the electrocatalytic performance for the OER while focusing on the prolonged electrochemical activation process. Two ALD methods, namely, plasma-assisted and thermal ALD, are employed as tools to deposit NiO films. Cyclic voltammetry analysis of ∼10 nm films in 1.0 M KOH solution reveals a multistep electrochemical activation process accompanied by phase transformation and delamination of activated nanostructures. The plasma-assisted ALD NiO film exhibits three times higher current density at 1.8 V vs RHE than its thermal ALD counterpart due to enhanced β-NiOOH formation during activation, thereby improving the OER activity. Additionally, the rougher surface formed during activation enhanced the overall catalytic activity of the films. The goal is to unravel the relationship between material properties and the performance of the resulting OER, specifically focusing on how the design of the material by ALD can lead to the enhancement of its electrocatalytic performance., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

In this work, two industrial dual-step pressure swing adsorption (PSA) processes were designed and simulated to obtain high-purity methane, CO 2 , and syngas from a gas effluent of a CO 2 electroreduction reactor using different design configurations. Among the set of zeolites that was investigated using Monte Carlo and molecular dynamics simulations, NaX and MFI were the ones selected. The dual-PSA process for case study 1 is only capable of achieving a 90.5% methane purity with a 95.2% recovery. As for case study 2, methane is obtained with a 97.5% purity and 95.3% recovery. Both case studies can produce CO 2 with high purity and recovery (>97 and 95%, respectively) and syngas with a H 2 /CO ratio above 4. Although case study 2 allows methane to be used as domestic gas, a much higher value for its energy consumption is observed compared to case study 1 (64.9 vs 29.8 W h mol CH4 -1 )., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Optimized Pt-based methanol oxidation reaction (MOR) anodes are essential for commercial direct methanol fuel cells (DMFCs) and methanol electrolyzers for hydrogen production. High surface area Ti supports are known to increase Pt catalytic activity and utilization. Pt has been deposited on black titania nanotubes (bTNTs), Ti felts and, for comparison, Ti foils by a galvanic deposition process, whereby Pt(IV) from a chloroplatinate solution is spontaneously reduced to metallic Pt (at 65 °C) onto chemically reduced (by CaH 2 ) TNTs (resulting in bTNTs), chemically etched (HCl + NaF) Ti felts and grinded Ti foils. All Pt/Ti-based electrodes prepared by this method showed enhanced intrinsic catalytic activity towards MOR when compared to Pt and other Pt/Ti-based catalysts. The very high/high mass specific activity of Pt/bTNTs (ca 700 mA mg Pt -1 at the voltammetric peak of 5 mV s -1 in 0.5 M MeOH) and of Pt/Ti-felt (ca 60 mA mg Pt -1 , accordingly) make these electrodes good candidates for MOR anodes and/or reactive Gas Diffusion Layer Electrodes (GDLEs) in DMFCs and/or methanol electrolysis cells.

Protonic ceramic solid oxide cells (P-SOCs) have gained widespread attention due to their potential for operation in the temperature range of 300-500 °C, which is not only beneficial in terms of material stability but also offers unique possibilities from a thermodynamic point of view to realize a series of reactions. For instance, they are ideal for the production of synthetic fuels by hydrogenation of carbon dioxide and nitrogen, upgradation of hydrocarbons, or dehydrogenation reactions. However, the development of P-SOC is quite challenging because it requires a multifront optimization in terms of material synthesis and fabrication procedures. Herein, we report in detail a method to overcome various fabrication challenges for the development of efficient and robust electrode-supported P-SOCs (Ni-BCZY/BCZY/Ni-BCZY) based on a BaCe 0.2 Zr 0.7 Y 0.1 O 3-δ (BCZY271) electrolyte. We examined the effect of pore formers on the porosity of the Ni-BCZY support electrode, various electrolyte deposition techniques (spray, spin, and vacuum-assisted), and thermal treatments for developing robust and flat half-cells. Half-cells containing a thin (10-12 μm) pinhole-free electrolyte layer were completed by a screen-printed Ni-BCZY electrode and evaluated as an electrochemical hydrogen pump to access the functionality. The P-SOCs are found to show a current density ranging from 150 to 525 mA cm -2 at 1 V over an operating temperature range of 350-450 °C. The faradaic efficiency of the P-SOCs as well as their stability were also evaluated.

Heterogeneous catalysts coupled with non-thermal plasmas (NTP) are known to achieve reaction yields that exceed the contributions of the individual components. Rationalization of the enhancing potential of catalysts, however, remains challenging because the background contributions from NTP or catalysts are often non-negligible. Here, we first demonstrate platinum (Pt)-catalyzed nitrogen (N 2 ) oxidation in a radio frequency plasma afterglow at conditions at which neither catalyst nor plasma alone produces significant concentrations of nitric oxide (NO). We then develop reactor models based on reduced NTP- and surface-microkinetic mechanisms to identify the features of each that lead to the synergy between NTP and Pt. At experimental conditions, NTP and thermal catalytic NO production are suppressed by radical reactions and high N 2 dissociation barrier, respectively. Pt catalyzes NTP-generated radicals and vibrationally excited molecules to produce NO. The model construction further illustrates that the optimization of productivity and energy efficiency involves tuning of plasma species, catalysts properties, and the reactor configurations to couple plasma and catalysts. These results provide unambiguous evidence of synergism between plasma and catalyst, the origins of that synergy for N 2 oxidation, and a modeling approach to guide material selection and system optimization., (© 2022. The Author(s).)

Perovskite oxides with dispersed nanoparticles on their surface are considered instrumental in energy conversion and catalytic processes. Redox exsolution is an alternative method to the conventional deposition techniques for directly growing well-dispersed and anchored nanoarchitectures from the oxide support through thermochemical or electrochemical reduction. Herein, a new method for such nanoparticle nucleation through the exposure of the host perovskite to plasma is shown. The applicability of this new method is demonstrated by performing catalytic tests for CO 2 hydrogenation over Ni exsolved nanoparticles prepared by either plasma or conventional H 2 reduction. Compared to the conventional thermochemical H 2 reduction, there are plasma conditions that lead to the exsolution of a more than ten times higher Ni amount from a lanthanum titanate perovskite, which is similar to the reported values of the electrochemical method. Unlike the electrochemical method, however, plasma does not require the integration of the material in an electrochemical cell, and is thus applicable to a wide range of microstructures and physical forms. Additionally, when N 2 plasma is employed, the nitrogen species are stripping out oxygen from the perovskite lattice, generating a key chemical intermediate, such as NO, rendering this technology even more appealing., (© 2021 Wiley-VCH GmbH.)