Boosting the reaction kinetics in aprotic lithium-carbon dioxide batteries with unconventional phase metal nanomaterials.

Given the high energy density and eco-friendly characteristics, lithium-carbon dioxide (Li-CO2) batteries have been considered to be a next-generation energy technology to promote carbon neutral and space exploration. However, Li-CO2 batteries suffer from sluggish reaction kinetics, causing large overpotential and poor energy efficiency. Here, we observe enhanced reaction kinetics in aprotic Li-CO2 batteries with unconventional phase 4H/face-centered cubic (fcc) iridium (Ir) nanostructures grown on gold template. Significantly, 4H/fcc Ir exhibits superior electrochemical performance over fcc Ir in facilitating the round-trip reaction kinetics of Li+-mediated CO2 reduction and evolution, achieving a low charge plateau below 3.61 V and high energy efficiency of 83.8%. Ex situ/in situ studies and theoretical calculations reveal that the boosted reaction kinetics arises from the highly reversible generation of amorphous/low-crystalline discharge products on 4H/fcc Ir via the Ir-O coupling. The demonstration of flexible Li-CO2 pouch cells with 4H/fcc Ir suggests the feasibility of using unconventional phase nanomaterials in practical scenarios.

Metal Doped Unconventional Phase IrNi Nanobranches: Tunable Electrochemical Nitrate Reduction Performance and Pollutants Upcycling.

Electrochemical nitrate reduction (NO3RR) provides a new option to abate nitrate contamination with a low carbon footprint. Restricted by competitive hydrogen evolution, achieving satisfied nitrate reduction performance in neutral media is still a challenge, especially for the regulation of this multielectron multiproton reaction. Herein, facile element doping is adopted to tune the catalytic behavior of IrNi alloy nanobranches with an unconventional hexagonal close-packed (hcp) phase toward NO3RR. In particular, the obtained hcp IrNiCu nanobranches favor the ammonia production and suppress byproduct formation in a neutral electrolyte indicated by in situ differential electrochemical mass spectrometry, with a high Faradaic efficiency (FE) of 85.6% and a large yield rate of 1253 µg cm-2 h-1 at -0.4 and -0.6 V (vs reversible hydrogen electrode (RHE)), respectively. In contrast, the resultant hcp IrNiCo nanobranches promote the formation of nitrite, with a peak FE of 33.1% at -0.1 V (vs RHE). Furthermore, a hybrid electrolysis cell consisting of NO3RR and formaldehyde oxidation is constructed, which are both catalyzed by hcp IrNiCu nanobranches. This electrolyzer exhibits lower overpotential and holds the potential to treat polluted air and wastewater simultaneously, shedding light on green chemical production based on contaminate degradation.

Controlled Synthesis of Unconventional Phase Alloy Nanobranches for Highly Selective Electrocatalytic Nitrite Reduction to Ammonia.

The controlled synthesis of metal nanomaterials with unconventional phases is of significant importance to develop high-performance catalysts for various applications. However, it remains challenging to modulate the atomic arrangements of metal nanomaterials, especially the alloy nanostructures that involve different metals with distinct redox potentials. Here we report the general one-pot synthesis of IrNi, IrRhNi and IrFeNi alloy nanobranches with unconventional hexagonal close-packed (hcp) phase. Notably, the as-synthesized hcp IrNi nanobranches demonstrate excellent catalytic performance towards electrochemical nitrite reduction reaction (NO2RR), with superior NH3 Faradaic efficiency and yield rate of 98.2 % and 34.6 mg h-1 mgcat -1 (75.5 mg h-1 mgIr -1) at 0 and -0.1 V (vs reversible hydrogen electrode), respectively. Ex/in situ characterizations and theoretical calculations reveal that the Ir-Ni interactions within hcp IrNi alloy improve electron transfer to benefit both nitrite activation and active hydrogen generation, leading to a stronger reaction trend of NO2RR by greatly reducing energy barriers of rate-determining step.

Structural Transformation of Unconventional-Phase Materials.

The structural transformation of materials, which involves the evolution of different structural features, including phase, composition, morphology, etc., under external conditions, represents an important fundamental phenomenon and has drawn substantial research interest. Recently, materials with unconventional phases that are different from their thermodynamically stable ones have been demonstrated to possess distinct properties and compelling functions and can further serve as starting materials for structural transformation studies. The identification and mechanism study of the structural transformation process of unconventional-phase starting materials can not only provide deep insights into their thermodynamic stability in potential applications but also offer effective approaches for the synthesis of other unconventional structures. Here, we briefly summarize the recent research progress on the structural transformation of some typical starting materials with various unconventional phases, including the metastable crystalline phase, amorphous phase, and heterophase, induced by different approaches. The importance of unconventional-phase starting materials in the structural modulation of resultant intermediates and products will be highlighted. The employment of diverse in situ/operando characterization techniques and theoretical simulations in studying the mechanism of the structural transformation process will also be introduced. Finally, we discuss the existing challenges in this emerging research field and provide some future research directions.

Single Transition Metal Atom Bound to the Unconventional Phase of the MoS2 Monolayer for Catalytic Oxygen Reduction Reaction: A First-Principles Study.

Supported single-atom catalysts (SACs) have received a lot of attention due to their super-high atom utilization and outstanding catalytic performance. However, the instability of the supported transition-metal (TM) atoms hampers their widespread applications. Exploration of an appropriate substrate to stabilize the supported single atom is crucial for the future implementation of SACs. In recent years, two-dimensional materials have been proposed as possible substrates due to their large specific surface areas, but their chemically inert surfaces are difficult to stabilize TM atoms without defecting or doping. Herein, by means of systematic first-principles calculations, we demonstrate that the defect-free MoS2 monolayer in the unconventional phase (1T') can effectively immobilize single TM atoms owing to its unique electrophilic property as compared to the conventional 2H phase. As a prototype probe, we investigated oxygen reduction reaction (ORR) catalyzed by a total of 21 single TM atoms stabilized on 1T'-MoS2 and successfully screened out two candidates, Cu and Pd@1T'-MoS2, which have a low overpotential of 0.41 and 0.32 V respectively, outperforming most of the previously reported ORR catalysts. Furthermore, we reveal that the adsorption energy of the ORR intermediate, *OH, provides an excellent descriptor to assess the ORR activity, which is further determined by the d-band center of the supported TM adatoms, thus being a great advantage for future design of stable and high-performance SACs.