3D Dense Encapsulated Architecture of 2D Bi Nanosheets Enabling Potassium-Ion Storage with Superior Volumetric and Areal Capacities.

2D alloy-based anodes show promise in potassium-ion batteries (PIBs). Nevertheless, their low tap density and huge volume expansion cause insufficient volumetric capacity and cycling stability. Herein, a 3D highly dense encapsulated architecture of 2D-Bi nanosheets (HD-Bi@G) with conducive elastic networks and 3D compact encapsulation structure of 2D nano-sheets are developed. As expected, HD-Bi@G anode exhibits a considerable volumetric capacity of 1032.2 mAh cm-3, stable long-life span with 75% retention after 2000 cycles, superior rate capability of 271.0 mAh g-1 at 104 C, and high areal capacity of 7.94 mAh cm-2 (loading: 24.2 mg cm-2) in PIBs. The superior volumetric and areal performance mechanisms are revealed through systematic kinetic investigations, ex situ characterization techniques, and theorical calculation. The 3D high-conductivity elastic network with dense encapsulated 2D-Bi architecture effectively relieves the volume expansion and pulverization of Bi nanosheets, maintains internal 2D structure with fast kinetics, and overcome sluggish ionic/electronic diffusion obstacle of ultra-thick, dense electrodes. The uniquely encapsulated 2D-nanosheet structure greatly reduces K+ diffusion energy barrier and accelerates K+ diffusion kinetics. These findings validate a feasible approach to fabricate 3D dense encapsulated architectures of 2D-alloy nanosheets with conductive elastic networks, enabling the design of ultra-thick, dense electrodes for high-volumetric-energy-density energy storage.

Controllable Crystallization of Two-Dimensional Bi Nanocrystals with Morphology-Boosted CO2 Electroreduction in Wide pH Environments.

Two-dimensional low-melting-point (LMP) metal nanocrystals are attracting increasing attention with broad and irreplaceable applications due to their unique surface and topological structures. However, the chemical synthesis, especially the fine control over the nucleation (reduction) and growth (crystallization), of such LMP metal nanocrystals remains elusive as limited by the challenges of low standard redox potential, low melting point, poor crystalline symmetry, etc. Here, a controllable reduction-melting-crystallization (RMC) protocol to synthesize free-standing and surfactant-free bismuth nanocrystals with tunable dimensions, morphologies, and surface structures is presented. Especially, ultrathin bismuth nanosheets with flat or jagged surfaces/edges can be prepared with high selectivity. The jagged bismuth nanosheets, with abundant surface steps and defects, exhibit boosted electrocatalytic CO2 reduction performances in acidic, neutral, and alkaline aqueous solutions, achieving the maximum selectivity of near unity at the current density of 210 mA cm-2 for formate evolution under ambient conditions. This work creates the RMC pathway for the synthesis of free-standing two-dimensional LMP metal nanomaterials and may find broader applicability in more interdisciplinary applications.

Molten-Salt-Assisted Synthesis of Bismuth Nanosheets for Long-term Continuous Electrocatalytic Conversion of CO2 to Formate.

Two-dimensional (2D) monometallic pnictogens (antimony or Sb, and bismuth or Bi) nanosheets demonstrate potential in a variety of fields, including quantum devices, catalysis, biomedicine and energy, because of their unique physical, chemical, electronic and optical properties. However, the development of general and high-efficiency preparative routes toward high-quality pnictogen nanosheets is challenging. A general method involving a molten-salt-assisted aluminothermic reduction process is reported for the synthesis of Sb and Bi nanosheets in high yields (>90 %). Electrocatalytic CO2 reduction was investigated on the Bi nanosheets, and high catalytic selectively to formate was demonstrated with a considerable current density at a low overpotential and an impressive stability. Bi nanosheets continuously convert CO2 into formate in a flow cell operating for one month, with a yield rate of 787.5 mmol cm-2 h-1 . Theoretical results suggest that the edge sites of Bi are far more active than the terrace sites.

Generating Defect-Rich Bismuth for Enhancing the Rate of Nitrogen Electroreduction to Ammonia.

The electrochemical N2 fixation, which is far from practical application in aqueous solution under ambient conditions, is extremely challenging and requires a rational design of electrocatalytic centers. We observed that bismuth (Bi) might be a promising candidate for this task because of its weak binding with H adatoms, which increases the selectivity and production rate. Furthermore, we successfully synthesized defect-rich Bi nanoplates as an efficient noble-metal-free N2 reduction electrocatalyst via a low-temperature plasma bombardment approach. When exclusively using 1 H NMR measurements with N2 gas as a quantitative testing method, the defect-rich Bi(110) nanoplates achieved a 15 NH3 production rate of 5.453 µg mgBi -1 h-1 and a Faradaic efficiency of 11.68 % at -0.6 V vs. RHE in aqueous solution at ambient conditions.

Porous Bi Nanosheets Derived from ß-Bi2O3 for Efficient Electrocatalytic CO2 Reduction to Formate.

The electrochemical CO2 reduction reaction (ECO2RR) is a promising strategy for converting CO2 into high-value chemical products. However, the synthesis of effective and stable electrocatalysts capable of transforming CO2 into a specified product remains a huge challenge. Herein, we report a template-regulated strategy for the preparation of a Bi2O3-derived nanosheet catalyst with abundant porosity to achieve the expectantly efficient CO2-to-formate conversion. The resultant porous bismuth nanosheet (p-Bi) not only exhibited marked Faradaic efficiency of formate (FEformate), beyond 91% in a broad potential range from -0.75 to -1.1 V in the H-type cell, but also demonstrated an appreciable FEformate of 94% at a high current density of 262 mA cm-2 in the commercially important gas diffusion cell. State-of-the-art X-ray absorption near edge structure spectroscopy (XANES) and theoretical calculation unraveled the distinct formate production performance of the p-Bi catalyst, which was cocontributed by its smaller size, plentiful porous structure, and stronger Bi-O bond, thus accelerating the absorption of CO2 and promoting the subsequent formation of intermediates. This work provides an avenue to fabricate bismuth-based catalysts with high planar and porous morphologies for a broad portfolio of applications.

Bismuth Nanosheets Derived by In Situ Morphology Transformation of Bismuth Oxides for Selective Electrochemical CO2 Reduction to Formate.

Bismuth nanosheets (BiNSs) have been recognized as a promising catalyst for electrochemical CO2 reduction (CO2RR) to formate, but their preparation typically involves an elaborate synthesis of Bi precursors under elevated temperatures and pressures. Here, we demonstrate a simple surfactant-free method of preparing Bi2O3-derived BiNSs (OD-BiNSs) by aqueous precipitation and cyclic voltammetry (CV) under ambient conditions. In situ morphology transformation from Bi2O3 to BiNSs was observed during CV, in which the presence of oxygen and the initial morphology of Bi2O3 are crucial for the phase transformation. The as-prepared OD-BiNSs showed 93% of faradic efficiency (FE) to formate with a partial current density of 62 mA cm-2 at -0.95 VRHE in the H-cell and >94% FE at 50-200 mA cm-2 with cell voltages of 2.4-4.0 V in the flow cell.

Triple-Phase Interface Engineered Hierarchical Porous Electrode for CO2 Electroreduction to Formate.

The aqueous electrochemical CO2 reduction to valuable products is seen as one of the most promising candidates to achieve carbon neutrality yet still suffers from poor selectivity and lower current density. Highly efficient CO2 reduction significantly relies on well-constructed electrode to realize efficient and stable triple-phase contact of CO2 , electrolyte, and active sites. Herein, a triple-phase interface engineering approach featuring the combination of hierarchical porous morphology design and surface modification is presented. A hierarchical porous electrode is constructed by depositing bismuth nanosheet array on copper foam followed by trimethoxy (1H,1H,2H,2H-heptadecafluorodecyl) silane modification on the nanosheet surface. This electrode not only achieves highly selective and efficient CO2 reduction performance with formate selectivity above 90% over wide potentials and a partial current density over -90 mA cm-2 in H-cell but also maintains a superior stability during the long-term operation. It is demonstrated that this remarkable performance is attributed to the construction of efficient and stable triple-phase interface. Theoretical calculations also show that the modified surface optimizes the activation path by lowering thermodynamic barriers of the key intermediates *OCHO for the formation of formate during electrochemical CO2 reduction.

In Situ Bismuth Nanosheet Assembly for Highly Selective Electrocatalytic CO2 Reduction to Formate.

The reduction of carbon dioxide (CO2 ) into value-added fuels using an electrochemical method has been regarded as a compelling sustainable energy conversion technology. However, high-performance electrocatalysts for CO2 reduction reaction (CO2 RR) with high formate selectivity and good stability need to be improved. Earth-abundant Bi has been demonstrated to be active for CO2 RR to formate. Herein, we fabricated an extremely active and selective bismuth nanosheet (Bi-NSs) assembly via an in situ electrochemical transformation of (BiO)2 CO3 nanostructures. The as-prepared material exhibits high activity and selectivity for CO2 RR to formate, with nearly 94% faradaic efficiency at -1.03 V (versus reversible hydrogen electrode (vs. RHE)) and stable selectivity (>90%) in a large potential window ranging from -0.83 to -1.18 V (vs. RHE) and excellent durability during 12 h continuous electrolysis. In addition, the Bi-NSs based CO2 RR/methanol oxidation reaction (CO2 RR/MOR) electrolytic system for overall CO2 splitting was constructed, evidencing the feasibility of its practical implementation.

Hydrangea-like Superstructured Micro/Nanoreactor of Topotactically Converted Ultrathin Bismuth Nanosheets for Highly Active CO2 Electroreduction to Formate.

An electrocatalytic carbon dioxide reduction reaction (CO2RR) is an appealing route to obtain the value-added feedstocks and alleviate the energy crisis. However, how to achieve high-performance electrocatalysts for CO2 reduction to formate is challenging owing to the poor intrinsic activity, insufficient conductivity, and low surface density of active sites. Herein, we fabricated an extremely active and selective hydrangea-like superstructured micro/nanoreactor of ultrathin bismuth nanosheets through an in situ electrochemical topotactic transformation of hierarchical bismuth oxide formate (BiOCOOH). The resulted bismuth nanosheet superstructure is in the form of three-dimensional intercrossed networks of ultrathin nanosheets, forming an ordered open porous structure through self-assembly, which can be used as a micro/nanoreactor to enable a large electrochemically active surface area as well as high atomic utilization. Such a distinctive nanostructure endows the material with high electrocatalytic performances for CO2 reduction to formate with near-unity Faradaic selectivity (>95%) in a wide potential window from -0.78 to -1.18 V. Furthermore, this micro/nanoreactor can give the high current densities over 300 mA cm-2 at low applied potentials without compromising selectivity in a flow cell reactor. Density functional theory (DFT) and in situ attenuated total reflection-infrared spectroscopy (in situ ATR-IR) were further conducted to interpret the CO2RR mechanisms.