Breaking Scaling Relations for Highly Efficient Electroreduction of CO2 to CO on Atomically Dispersed Heteronuclear Dual-Atom Catalyst.

Conversion of CO2 into value-added products by electrocatalysis provides a promising way to mitigate energy and environmental problems. However, it is greatly limited by the scaling relationship between the adsorption strength of intermediates. Herein, Mn and Ni single-atom catalysts, homonuclear dual-atom catalysts (DACs), and heteronuclear DACs are synthesized. Aberration-corrected annular dark-field scanning transmission electron microscopy (ADF-STEM) and X-ray absorption spectroscopy characterization uncovered the existence of the Mn─Ni pair in Mn─Ni DAC. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy reveal that Mn donated electrons to Ni atoms in Mn─Ni DAC. Consequently, Mn─Ni DAC displays the highest CO Faradaic efficiency of 98.7% at -0.7 V versus reversible hydrogen electrode (vs RHE) with CO partial current density of 16.8 mA cm-2. Density functional theory calculations disclose that the scaling relationship between the binding strength of intermediates is broken, resulting in superior performance for ECR to CO over Mn─Ni─NC catalyst.

The Native Oxide Skin of Liquid Metal Ga Nanoparticles Prevents Their Rapid Coalescence during Electrocatalysis.

Liquid metals (LMs) have been used in electrochemistry since the 19th century, but it is only recently that they have emerged as electrocatalysts with unique properties, such as inherent resistance to coke poisoning, which derives from the dynamic nature of their surface. The use of LM nanoparticles (NPs) as electrocatalysts is highly desirable to enhance any surface-related phenomena. However, LM NPs are expected to rapidly coalesce, similarly to liquid drops, which makes their implementation in electrocatalysis hard to envision. Herein, we demonstrate that liquid Ga NPs (18 nm, 26 nm, 39 nm) drive the electrochemical CO2 reduction reaction (CO2RR) while remaining well-separated from each other. CO is generated with a maximum faradaic efficiency of around 30% at -0.7 VRHE, which is similar to that of bulk Ga. The combination of electrochemical, microscopic, and spectroscopic techniques, including operando X-ray absorption, indicates that the native oxide skin of the Ga NPs is still present during CO2RR and provides a barrier to coalescence during operation. This discovery provides an avenue for future development of Ga-based LM NPs as a new class of electrocatalysts.

Cation-Deficient Ce-Substituted Perovskite Oxides with Dual-Redox Active Sites for Thermochemical Applications.

Identifying thermodynamically favorable and stable non-stoichiometric metal oxides is of crucial importance for solar thermochemical (STC) fuel production via two-step redox cycles. The performance of a non-stoichiometric metal oxide depends on its thermodynamic properties, oxygen exchange capacity, and its phase stability under high-temperature redox cycling conditions. Perovskite oxides (ABO3-δ) are being considered as attractive alternatives to the state-of-the-art ceria (CeO2-δ) due to their high thermodynamic and structural tunability. However, perovskite oxides often exhibit low entropy change compared to ceria, as they generally have one only redox active site, leading to lower mass-specific fuel yields. Herein, we investigate cation-deficient Ce-substituted perovskite oxides as a new class of potential redox materials combining the advantages of perovskites and ceria. We newly synthesized the (CexSr1-x)0.95Ti0.5Mn0.5O3-δ (x = 0, 0.10, 0.15, and 0.20; CSTM) series, with dual-redox active sites comprising Ce (at the A-site) and Mn (at the B-site). By introducing a cation deficiency (∼5%), CSTM perovskite oxides with both phase purity (x ≤ 0.15) and high-temperature structural stability under STC redox cycling conditions are obtained. Thermodynamic properties are evaluated by measuring oxygen non-stoichiometry in the temperature range T = 700-1400 °C and the oxygen partial pressure range pO2 = 1-10-4 bar. The results demonstrate that CSTM perovskite oxides exhibit a composition-dependent simultaneous increase of enthalpy and entropy change with increasing Ce-substitution. (Ce0.20Sr0.80)0.95Ti0.5Mn0.5O3-δ (CSTM20) showed a combination of large entropy change of ∼141 J (mol-O)-1 K-1 and moderate enthalpy change of ∼238 kJ (mol-O)-1, thereby creating favorable conditions for thermochemical H2O splitting. Furthermore, the oxidation states and local coordination environment around Mn, Ce, and Ti sites in the pristine and reduced CSTM samples were extensively studied using X-ray absorption spectroscopy. The results confirmed that both Ce (at the A-site) and Mn (at the B-site) centers undergo simultaneous reduction during thermochemical redox cycling.