Constructing Gradient Orbital Coupling to Induce Reactive Metal-Support Interaction in Pt-Carbide Electrocatalysts for Efficient Methanol Oxidation.

Reactive metal-support interaction (RMSI) is an emerging way to regulate the catalytic performance for supported metal catalysts. However, the induction of RMSI by the thermal reduction is often accompanied by the encapsulation effect on metals, which limits the mechanism research and applications of RMSI. In this work, a gradient orbital coupling construction strategy was successfully developed to induce RMSI in Pt-carbide system without a reductant, leading to the formation of L12-PtxM-MCy (M = Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W) intermetallic electrocatalysts. Density functional theory (DFT) calculations suggest that the gradient coupling of the d(M)-2p(C)-5d(Pt) orbital would induce the electron transfer from M to C covalent bonds to Pt NPs, which facilitates the formation of C vacancy (Cv) and the subsequent M migration (occurrence of RMSI). Moreover, the good correlation between the formation energy of Cv and the onset temperature of RMSI in Pt-MCx systems proves the key role of nonmetallic atomic vacancy formation for inducing RMSI. The developed L12-Pt3Ti-TiC catalyst exhibits excellent acidic methanol oxidation reaction activity, with mass activity of 2.36 A mgPt-1 in half-cell and a peak power density of 187.9 mW mgPt-1 in a direct methanol fuel cell, which is one of the best catalysts ever reported. DFT calculations reveal that L12-Pt3Ti-TiC favorably weakens *CO absorption compared to Pt-TiC due to the change of the absorption site from Pt to Ti, which accounts for the enhanced MOR performance.

In Situ Self-Assembled Active and Stable Ir@MnOx/La0.7Sr0.3Cr0.9Ir0.1O3-δ Interfaces for CO2 Electrolysis.

Solid oxide electrolysis cells are prospective approaches for CO2 utilization but face significant challenges due to the sluggish reaction kinetics and poor stability of the fuel electrodes. Herein, we strategically addressed the long-standing trade-off phenomenon between enhanced exsolution and improved structural stability via topotactic ion exchange. The surface dynamic reconstruction of the MnOx/La0.7Sr0.3Cr0.9Ir0.1O3-δ (LSCIr) catalyst was visualized at the atomic scale. Compared with the Ir@LSCIr interface, the in situ self-assembled Ir@MnOx/LSCIr interface exhibited greater CO2 activation and easily removable carbonate intermediates, thus reached a 42 % improvement in CO2 electrolysis performance at 1.6 V. Furthermore, an improved CO2 electrolysis stability was achieved due to the uniformly wrapped MnOx shell of the Ir@MnOx/LSCIr cathode. Our approach enables a detailed understanding of the dynamic microstructure evolution at active interfaces and provides a roadmap for the rational design and evaluation of efficient metal/oxide catalysts for CO2 electrolysis.

Metal bond strength regulation enables large-scale synthesis of intermetallic nanocrystals for practical fuel cells.

Structurally ordered L10-PtM (M = Fe, Co, Ni and so on) intermetallic nanocrystals, benefiting from the chemically ordered structure and higher stability, are one of the best electrocatalysts used for fuel cells. However, their practical development is greatly plagued by the challenge that the high-temperature (>600 °C) annealing treatment necessary for realizing the ordered structure usually leads to severe particle sintering, morphology change and low ordering degree, which makes it very difficult for the gram-scale preparation of desirable PtM intermetallic nanocrystals with high Pt content for practical fuel cell applications. Here we report a new concept involving the low-melting-point-metal (M' = Sn, Ga, In)-induced bond strength weakening strategy to reduce Ea and promote the ordering process of PtM (M = Ni, Co, Fe, Cu and Zn) alloy catalysts for a higher ordering degree. We demonstrate that the introduction of M' can reduce the ordering temperature to extremely low temperatures (≤450 °C) and thus enable the preparation of high-Pt-content (≥40 wt%) L10-Pt-M-M' intermetallic nanocrystals as well as ten-gram-scale production. X-ray spectroscopy studies, in situ electron microscopy and theoretical calculations reveal the fundamental mechanism of the Sn-facilitated ordering process at low temperatures, which involves weakened bond strength and consequently reduced Ea via Sn doping, the formation and fast diffusion of low-coordinated surface free atoms, and subsequent L10 nucleation. The developed L10-Ga-PtNi/C catalysts display outstanding performance in H2-air fuel cells under both light- and heavy-duty vehicle conditions. Under the latter condition, the 40% L10-Pt50Ni35Ga15/C catalyst delivers a high current density of 1.67 A cm-2 at 0.7 V and retains 80% of the current density after extended 90,000 cycles, which exceeds the United States Department of Energy performance metrics and represents among the best cathodic electrocatalysts for practical proton-exchange membrane fuel cells.

In situ electrochemical reconstruction of Sr2Fe1.45Ir0.05Mo0.5O6-δ perovskite cathode for CO2 electrolysis in solid oxide electrolysis cells.

Solid oxide electrolysis cells provide a practical solution for the direct conversion of CO2 to other chemicals (i.e. CO), however, an in-depth mechanistic understanding of the dynamic reconstruction of active sites for perovskite cathodes during CO2 electrolysis remains a great challenge. Herein, we identify that iridium-doped Sr2Fe1.45Ir0.05Mo0.5O6-δ (SFIrM) perovskite displays a dynamic electrochemical reconstruction feature during CO2 electrolysis with abundant exsolution of highly dispersed IrFe alloy nanoparticles on the SFIrM surface. The in situ reconstructed IrFe@SFIrM interfaces deliver a current density of 1.46 A cm-2 while maintaining over 99% CO Faradaic efficiency, representing a 25.8% improvement compared with the Sr2Fe1.5Mo0.5O6-δ counterpart. In situ electrochemical spectroscopy measurements and density functional theory calculations suggest that the improved CO2 electrolysis activity originates from the facilitated formation of carbonate intermediates at the IrFe@SFIrM interfaces. Our work may open the possibility of using an in situ electrochemical poling method for CO2 electrolysis in practice.

A Reconstructed Cu2 P2 O7 Catalyst for Selective CO2 Electroreduction to Multicarbon Products.

The electrochemical CO2 reduction reaction (CO2 RR) over Cu-based catalysts shows great potential for converting CO2 into multicarbon (C2+ ) fuels and chemicals. Herein, we introduce an A2 M2 O7 structure into a Cu-based catalyst through a solid-state reaction synthesis method. The Cu2 P2 O7 catalyst is electrochemically reduced to metallic Cu with a significant structure evolution from grain aggregates to highly porous structure under CO2 RR conditions. The reconstructed Cu2 P2 O7 catalyst achieves a Faradaic efficiency of 73.6 % for C2+ products at an applied current density of 350 mA cm-2 , remarkably higher than the CuO counterparts. The reconstructed Cu2 P2 O7 catalyst has a high electrochemically active surface area, abundant defects, and low-coordinated sites. In situ Raman spectroscopy and density functional theory calculations reveal that CO adsorption with bridge and atop configurations is largely improved on Cu with defects and low-coordinated sites, which decreased the energy barrier of the C-C coupling reaction for C2+ products.

Promoting exsolution of RuFe alloy nanoparticles on Sr2Fe1.4Ru0.1Mo0.5O6-δ via repeated redox manipulations for CO2 electrolysis.

Metal nanoparticles anchored on perovskite through in situ exsolution under reducing atmosphere provide catalytically active metal/oxide interfaces for CO2 electrolysis in solid oxide electrolysis cell. However, there are critical challenges to obtain abundant metal/oxide interfaces due to the sluggish diffusion process of dopant cations inside the bulk perovskite. Herein, we propose a strategy to promote exsolution of RuFe alloy nanoparticles on Sr2Fe1.4Ru0.1Mo0.5O6-δ perovskite by enriching the active Ru underneath the perovskite surface via repeated redox manipulations. In situ scanning transmission electron microscopy demonstrates the dynamic structure evolution of Sr2Fe1.4Ru0.1Mo0.5O6-δ perovskite under reducing and oxidizing atmosphere, as well as the facilitated CO2 adsorption at RuFe@Sr2Fe1.4Ru0.1Mo0.5O6-δ interfaces. Solid oxide electrolysis cell with RuFe@Sr2Fe1.4Ru0.1Mo0.5O6-δ interfaces shows over 74.6% enhancement in current density of CO2 electrolysis compared to that with Sr2Fe1.4Ru0.1Mo0.5O6-δ counterpart as well as impressive stability for 1000 h at 1.2 V and 800 °C.

Atomic-Scale Insight into Exsolution of CoFe Alloy Nanoparticles in La0.4 Sr0.6 Co0.2 Fe0.7 Mo0.1 O3-δ with Efficient CO2 Electrolysis.

In situ exsolution of metal nanoparticles in perovskite under reducing atmosphere is employed to generate a highly active metal-oxide interface for CO2 electrolysis in a solid oxide electrolysis cell. Atomic-scale insight is provided into the exsolution of CoFe alloy nanoparticles in La0.4 Sr0.6 Co0.2 Fe0.7 Mo0.1 O3-δ (LSCFM) by in situ scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy and DFT calculations. The doped Mo atoms occupy B sites of LSCFM, which increases the segregation energy of Co and Fe ions at B sites and improves the structural stability of LSCFM under a reducing atmosphere. In situ STEM measurements visualized sequential exsolution of Co and Fe ions, formation of CoFe alloy nanoparticles, and reversible exsolution and dissolution of CoFe alloy nanoparticles in LSCFM. The metal-oxide interface improves CO2 adsorption and activation, showing a higher CO2 electrolysis performance than the LSCFM counterparts.

Platinum-Decorated Ceria Enhances CO2 Electroreduction in Solid Oxide Electrolysis Cells.

CO2 electroreduction by solid oxide electrolysis cells (SOECs) can not only attenuate the greenhouse effect, but also convert surplus electrical energy into chemical energy. The adsorption and activation of CO2 on the cathode play an important role in the SOEC performance. La0.6 Sr0.4 Co0.2 Fe0.8 O3-δ -Ce0.8 Sm0.2 O2-δ (LSCF-SDC; SDC=samarium-doped ceria) is a promising SOEC cathode. However, its electrocatalytic activity still needs to be improved. In this study, Pt/SDC interfaces are constructed by decorating Pt nanoparticles onto the SDC surface. Electrochemical measurements indicate that the polarization resistance of the SOEC is decreased from 0.308 to 0.120â€…Ω cm2 , and the current density is improved from 0.913 to 1.420 A cm-2 at 1.6 V and 800 °C. Physicochemical characterizations suggest that construction of the Pt/SDC interfaces increases the oxygen vacancy concentration on the cathode and boosts CO2 adsorption and dissociation, which leads to enhanced CO2 electroreduction performance in SOECs.

In Situ Investigation of Reversible Exsolution/Dissolution of CoFe Alloy Nanoparticles in a Co-Doped Sr2 Fe1.5 Mo0.5 O6- δ Cathode for CO2 Electrolysis.

Reversible exsolution and dissolution of metal nanoparticles in perovskite has been investigated as an efficient strategy to improve CO2 electrolysis performance. However, fundamental understanding with regard to the reversible exsolution and dissolution of metal nanoparticles in perovskite is still scarce. Herein, in situ exsolution and dissolution of CoFe alloy nanoparticles in Co-doped Sr2 Fe1.5 Mo0.5 O6-δ (SFMC) revealed by in situ X-ray diffraction, scanning transmission electron microscopy, environmental scanning electron microscopy, and density functional theory calculations are reported. Under a reducing atmosphere, facile exsolution of Co promotes reduction of the Fe cation to generate CoFe alloy nanoparticles in SFMC, accompanied by structure transformation from double perovskite to layered perovskite at 800 °C. Under an oxidizing atmosphere, spherical CoFe alloy nanoparticles are first oxidized to flat CoFeOx nanosheets, and then dissolved into the bulk with structure evolution from layered perovskite back to double perovskite. Electrochemically, CO2 electrolysis performance can be retrieved during 12 redox cycles due to the regenerative ability of the CoFe alloy nanoparticles. The anchoring of the CoFe alloy nanoparticles in SFMC perovskite via reduction shows enhanced CO2 electrolysis performance and stability compared with the parent SFMC perovskite.

Interfacial Enhancement by γ-Al2 O3 of Electrochemical Oxidative Dehydrogenation of Ethane to Ethylene in Solid Oxide Electrolysis Cells.

Oxidative dehydrogenation of ethane (ODE) is limited by the facile deep oxidation and potential safety hazards. Now, electrochemical ODE reaction is incorporated into the anode of a solid oxide electrolysis cell, utilizing the oxygen species generated at anode to catalytically convert ethane. By infiltrating γ-Al2 O3 onto the surface of La0.6 Sr0.4 Co0.2 Fe0.8 O3-δ -Sm0.2 Ce0.8 O2-δ (LSCF-SDC) anode, the ethylene selectivity reaches as high as 92.5 %, while the highest ethane conversion is up to 29.1 % at 600 °C with optimized current and ethane flow rate. Density functional theory calculations and in situ X-ray photoelectron spectroscopy characterizations reveal that the Al2 O3 /LSCF interfaces effectively reduce the amount of adsorbed oxygen species, leading to improved ethylene selectivity and stability, and that the formation of Al-O-Fe alters the electronic structure of interfacial Fe center with increased density of state around Fermi level and downshift of the empty band, which enhances ethane adsorption and conversion.