Dealloying-Derived Self-Supporting Nanoporous Zinc Film with Optimized Macro/Microstructure for High-Performance Solar Steam Generation.

Solar steam generation (SSG) is a promising technology for the production of freshwater that can help alleviate global water scarcity. Nanostructured metals, known for their localized surface plasmon resonance effect, have generated significant interest, but low-cost metal films with excellent water evaporation properties are challenging. In this work, we present a one-step dealloying route for fabricating self-supporting black nanoporous zinc (NP-Zn) films with a bicontinuous ligament/channel structure, using Al-Zn solid solution alloys as the precursors. The influence of alloy composition on the formation and macro/microstructure of NP-Zn was investigated, and an optimal Al98Zn2 was selected. Additionally, in situ and ex situ characterizations were conducted to unveil the dealloying mechanism of Al98Zn2 and phase/microstructure evolution of NP-Zn during dealloying, including the phase transition of Al(Zn) → Zn, significant volume shrinkage (89.8%), and the development of high porosity (81.3%). The nanoscale ligament/channel structure and high porosity endow the NP-Zn films with good broadband absorption and superior hydrophilicity and, more importantly, give them excellent SSG performance. The NP-Zn2 film displays high evaporation efficiency, superior stability, and good seawater desalination performance. The efficient SSG performance, material abundance, and low cost suggest that NP-Zn films have promising applications in metal-based photothermal materials for SSG.

Maximum Impact of Ionic Strength on Acid-Catalyzed Reaction Rates Induced by a Zeolite Microporous Environment.

The intracrystalline ionic environment in microporous zeolite can remarkably modify the excess chemical potential of adsorbed reactants and transition states, thereby influencing the catalytic turnover rates. However, a limit of the rate enhancement for aqueous-phase dehydration of alcohols appears to exist for zeolites with high ionic strength. The origin of such limitation has been hypothesized to be caused by the spatial constraints in the pores via, e.g., size exclusion effects. It is demonstrated here that the increase in turnover rate as well as the formation of a maximum and the rate drop are intrinsic consequences of the increasingly dense ionic environment in zeolite. The molecularly sized confines of zeolite create a unique ionic environment that monotonically favors the formation of alcohol-hydronium ion complexes in the micropores. The zeolite microporous environment determines the kinetics of catalytic steps and tailors the impact of ionic strength on catalytic rates.

Importance of interface open circuit potential on aqueous hydrogenolytic reduction of benzyl alcohol over Pd/C.

The open circuit potential (OCP) established by the quasi-equilibrated electrode reaction of H2 and H3O+(hydr.), complicates catalytic reactions significantly. The hydrogenolysis rate of benzylic alcohol on Pd/C increases 2-3 orders of magnitude with the pH decreasing from 7 to 0.6. The reaction follows a pathway of protonated benzyl alcohol dehydration to a benzylic carbenium ion, followed by a hydride addition to form toluene. The dehydration of protonated benzyl alcohol is kinetic relevent, thus, being enhanced at lower pH. The OCP stabilizes all cationic species in the elementary steps. Particularly, the initial state (benzyl alcohol oxonium ion) is less stabilized than the dehydration transition state and the product (benzylic carbenium), thus, lowering the free energy barrier of the rate-determining step. In accordance, the rate increased with increasingly negative OCP. Beside OCP, an external negative electric potential in an electrocatlaytic system was also demonstrated to enhance the rate in the same way.

Impact of hydronium ions on the Pd-catalyzed furfural hydrogenation.

In aqueous mediums, the chemical environment for catalytic reactions is not only comprised of water molecules but also of corresponding ionized species, i.e., hydronium ions, which can impact the mechanism and kinetics of a reaction. Here we show that in aqueous-phase hydrogenation of furfural on Pd/C, increasing the hydronium ion activities by five orders of magnitude (from pH 7 to pH 1.6) leads to an increase of less than one order of magnitude in the reaction rate. Instead of a proton-coupled electron transfer pathway, our results show that a Langmuir-Hinshelwood mechanism describes the rate-limiting hydrogen addition step, where hydrogen atom adsorbed on Pd is transferred to the carbonyl C atom of the reactant. As such, the strength of hydrogen binding on Pd, which decreases with increasing hydronium ion concentration (i.e., 2 kJ molH2-1 per unit pH), is a decisive factor in hydrogenation kinetics (rate constant +270%). In comparison, furfural adsorption on Pd is pH-independent, maintaining a tilted geometry that favors hydrogen attack at the carbonyl group over the furan ring.

High Throughput Preparation of Ag-Zn Alloy Thin Films for the Electrocatalytic Reduction of CO2 to CO.

Ag-Zn alloys are identified as highly active and selective electrocatalysts for CO2 reduction reaction (CO2RR), while how the phase composition of the alloy affects the catalytic performances has not been systematically studied yet. In this study, we fabricated a series of Ag-Zn alloy catalysts by magnetron co-sputtering and further explored their activity and selectivity towards CO2 electroreduction in an aqueous KHCO3 electrolyte. The different Ag-Zn alloys involve one or more phases of Ag, AgZn, Ag5Zn8, AgZn3, and Zn. For all the catalysts, CO is the main product, likely due to the weak CO binding energy on the catalyst surface. The Ag5Zn8 and AgZn3 catalysts show a higher CO selectivity than that of pure Zn due to the synergistic effect of Ag and Zn, while the pure Ag catalyst exhibits the highest CO selectivity. Zn alloying improves the catalytic activity and reaction kinetics of CO2RR, and the AgZn3 catalyst shows the highest apparent electrocatalytic activity. This work found that the activity and selectivity of CO2RR are highly dependent on the element concentrations and phase compositions, which is inspiring to explore Ag-Zn alloy catalysts with promising CO2RR properties.

Dealloying-Derived Nanoporous Bismuth for Selective CO2 Electroreduction to Formate.

Electrochemical CO2 reduction (CO2ER) to formate is an attractive approach for CO2 utilization. Here, we report a nanoporous bismuth (np-Bi) catalyst fabricated by chemically dealloying a rapidly solidified Mg92Bi8 alloy for CO2ER. The np-Bi catalyst exhibits a three-dimensional interconnected ligament-channel network structure, which can efficiently convert CO2 to formate with a selectivity of ≤94% and an activity of 62 mA cm-2 in a wide potential range. Remarkably, the np-Bi catalyst delivers an industry-level current density of ∼500 mA cm-2 for formate production at a low overpotential of 420 mV in the flow cell. The outstanding CO2ER performance can be attributed to the enlarged surface area with abundant accessible active sites and highly curved surfaces with enhanced intrinsic activity. This work highlights the structural synergies for enhancing CO2ER.

Electrochemically Tunable Proton-Coupled Electron Transfer in Pd-Catalyzed Benzaldehyde Hydrogenation.

Acid functionalization of a carbon support allows to enhance the electrocatalytic activity of Pd to hydrogenate benzaldehyde to benzyl alcohol proportional to the concentration of Brønsted-acid sites. In contrast, the hydrogenation rate is not affected when H2 is used as a reduction equivalent. The different responses to the catalyst properties are shown to be caused by differences in the hydrogenation mechanism between the electrochemical and the H2 -induced hydrogenation pathways. The enhancement of electrocatalytic reduction is realized by the participation of support-generated hydronium ions in the proximity of the metal particles.