Metallic Bi Research Articles

Bi Dendrites Succeed Under Challenging Flue Gas Conditions for CO2RR

AbstractThe electrochemical reduction of carbon dioxide (ERC) from flue gas is a promising solution to mitigate CO2 emissions and importantly has the ability for direct industrial application. However, components such as N2, O2, SOx, NOx, and H2O in flue gas can hinder ERC efficiency, affecting catalyst stability and selectivity. This study systematically investigates the effect of these flue gas components on a metallic Bi dendrite catalyst. The catalyst shows remarkable stability (over 6 days are observed with constant current generation) surpassing other monometallic Bi catalysts. The active state of the catalyst has been demonstrated with operando XANES (X‐ray Absorption Near Edge Structure) analysis which has confirmed the metallic state of bismuth and notably, the catalyst performance remains unaffected despite the presence of other flue gas components such as N2, O2, SOx, and NOx. This research aims to fill a critical gap, demonstrating how flue gas components influence ERC activity and pave the way for future advancements in catalyst optimization.

Low Temperature Atomic Layer Deposition of (00l)‐Oriented Elemental Bismuth

This study presents the first successful demonstration of growing elemental bismuth (Bi) thin films via thermal atomic layer deposition (ALD) using Bi(NMe2)3 as the precursor and Sb(SiMe3)3 as the co‐reactant. The films were deposited at a relatively low temperature of 100 °C, with a growth per cycle (GPC) of 0.31‐0.34 Å/cycle. Island formation marked the initial growth stages, with surface coverage reaching around 80% after 1000 cycles and full coverage between 2000 and 2500 cycles. Morphological analysis revealed that the Bi grains expanded and became more defined as the number of ALD cycles increased. This coalescence is further supported by X‐ray diffraction (XRD) patterns, which show a preferential shift in growth orientation from the (012) plane to the (003) plane as the film thickness increases. X‐ray photoemission spectroscopy (XPS) confirmed the presence of metallic Bi with minimal surface oxidation. Temperature‐dependent sheet resistance measurements highlight the semimetallic nature of Bi, with a room temperature resistivity of ≈200 µΩcm for the 2500 cycles Bi. Temperature‐dependent sheet resistance was also associated with a transition in carrier‐type dominance from electrons at higher temperatures to holes at lower temperatures.

Low Temperature Atomic Layer Deposition of (00l)-Oriented Elemental Bismuth.

This study presents the first successful demonstration of growing elemental bismuth (Bi) thin films via thermal atomic layer deposition (ALD) using Bi(NMe2)3 as the precursor and Sb(SiMe3)3 as the co-reactant. The films were deposited at a relatively low temperature of 100 °C, with a growth per cycle (GPC) of 0.31-0.34 Å/cycle. Island formation marked the initial growth stages, with surface coverage reaching around 80% after 1000 cycles and full coverage between 2000 and 2500 cycles. Morphological analysis revealed that the Bi grains expanded and became more defined as the number of ALD cycles increased. This coalescence is further supported by X-ray diffraction (XRD) patterns, which show a preferential shift in growth orientation from the (012) plane to the (003) plane as the film thickness increases. X-ray photoemission spectroscopy (XPS) confirmed the presence of metallic Bi with minimal surface oxidation. Temperature-dependent sheet resistance measurements highlight the semimetallic nature of Bi, with a room temperature resistivity of ≈200 µΩcm for the 2500 cycles Bi. Temperature-dependent sheet resistance was also associated with a transition in carrier-type dominance from electrons at higher temperatures to holes at lower temperatures.

Microstructure modulation improving stability performance of Bi anode for lithium-ion batteries

Metal Bi is a classic metal-type anode material characterized by its high volume-specific capacity (3785 mAh cm-3) and theoretical specific capacity (386 mAh g-1). However, during the charge and discharge...

In-situ designed Bi metal @ defective Bi2O2SO4 to enhance photocatalytic NO removal via boosted directional interfacial charge transfer.

Photocatalytic technology provides a new approach for the harmless treatment of low concentration NOx in the atmosphere. The development of high-performance semiconductor materials to improve the light absorption efficiency and the separation efficiency of photogenerated carriers is the focus of the research. Bismuth oxybismuth sulfate (Bi2O2SO4) shows significant potential for photocatalytic NOx purification due to its unique electronic and layered structure. However, its wide bandgap limits light absorption efficiency in the visible region, resulting in an undesirable photocatalytic activity. The surface plasmon resonance effect presents an effective strategy to enhance the catalytic activity of wide bandgap semiconductors under visible light. In this study, metal Bi loaded Bi2O2SO4 photocatalysts with abundant oxygen vacancies (OVs) were prepared by in-situ reduction with NaBH4, which exhibited a significantly enhanced visible-light catalytic purification of NO. The OVs not only induced the formation of intermediate energy levels and reduced the bandgap, but also enhanced the visible-light absorption ability of Bi2O2SO4 and promoted carrier separation. The Bi metal also promoted the carrier separation and provided more hot electrons for the activation of small molecules to generate reactive radicals, which facilitated the photocatalytic reaction. The photocatalytic NO purification pathway and its performance enhancement mechanism were investigated by combining theoretical calculations and in-situ infrared characterization. This work provides new insights for the development and design of novel Bi-based semiconductors and new materials for the application of low concentration NOx photocatalytic purification process.

Ultralow Lattice Thermal Conductivity and High ZT Beyond 1 Realized in Bi2S3 Nanocomposites via Bottom-Up Structure Design.

Bismuth sulfides (Bi2S3), an n-type thermoelectric material, in expensive, and environmentally friendly. However, it has poor electrical conductivity due to its low electron concentration, and its thermoelectric properties need improvement. By adjusting the properties of microstructural units and then designing and preparing bulk materials, the transport properties are modulated to optimize thermoelectric properties. The textured structure and metal Bi dispersed in grain boundaries improved the carrier mobility, the Cl dopingimproved carrier concentration. The textured structure and metalBi dispersed in grain boundaries improved the carrier mobility, the Cl dopingimproved carrier concentration. The Bi2S3-Cl samples reduce using N2H4·H2O for 5 min at 673 K have a peak power factor (PF) reaching 676.6 µWm-1K-2, more than 6 times that of pristine Bi2S3. Furthermore, the point defects, dislocations, and the micropores caused by a part of Bivolatilization contribute to the strong phonon scattering, resulting in a low lattice thermal conductivity of 0.28 Wm-1K-1 at 623K. Due to the synergistically optimized electrical and thermal transport properties, the values of the maximum thermoelectric figure of merit (ZTmax) and the average thermoelectric figure of merit (ZTave) for the Bi2S3-Cl samples reduce using N2H4·H2O for 5 min are 1.01 at ≈673 K and 0.63 (323-673 K), respectively. This study demonstrates that bottom-up structure design can effectively strategize the improvement of thermoelectric performance.

Unlocking the In Situ Reconstruction of Bi/Bi2O2CO3 Electrocatalyst Toward Efficiently Converting CO2 into Formate

AbstractElectrochemical reducing CO2 into formic acid has been demonstrated to be an economically viable pathway to relieve the greenhouse effect and obtain value‐added chemical feedstocks. Herein, Bi/Bi2O2CO3 is developed via the combination of sulfur‐assisted disassembly and an in situ reconstruction process. Profiting from the enlarged surface area and the generation of the high active heterointerface between metallic Bi and Bi2O2CO3, the as‐obtained Bi/Bi2O2CO3 exhibits high performance toward converting CO2 molecules into formate (HCOO−), attaining the HCOO− Faradaic efficiency (FEHCOO‐) over 97% in the current density range from 200 to 1000 mA cm−2 in both alkaline (1 m KOH) and near neutral (0.5 m KHCO3) electrolytes, along with excellent stability. In situ spectroscopic data unraveled the reconstruction process from Bi2S3/Bi2O2CO3 to Bi/Bi2O2CO3 and corroborated that the conversion of CO2 into formate is through the *OCHO intermediate, deepening the insights into the understanding of the Bi‐based electrocatalyst reconstruction and CO2RR mechanism.

Coaxially Bi/ZnO@ZnSe Array Photocathode Enables Highly Efficient CO2 to C1 Conversion via Long-lived High-energy Photoelectrons.

The key aspect of the photoelectrochemical CO2 reduction reaction (PEC CO2 RR) lies in designing cathode materials that can generate high-energy photoelectrons, enabling the activation and conversion of CO2 into high-value products. In this study, a coaxially wrapped ZnO@ZnSe array heterostructure was synthesized using a simple anion exchange strategy and metallic Bi nanoparticles (NPs) were subsequently deposited on the surface to construct a Bi/ZnO@ZnSe photocathode with high CO2 conversion capability. This array photocathode possesses a large aspect ratio, which simultaneously satisfies a low charge carrier migration path and a large specific surface area that facilitates mass transfer. Additionally, the barrier formed at the n-n heterojunction interface hinders the transfer of high-energy photoelectrons from ZnSe to lower energy levels, resulting in their rapid capture by Bi while maintaining a relatively long lifetime. These captured electrons act as active sites, efficiently converting CO2 into CO with a Faradaic efficiency above 88.9 % at -0.9 V vs. RHE and demonstrating superior stability. This work provides a novel approach for synthesizing high-energy photoelectrode materials with long lifetimes.

Fermi energy level synergistic Bi-based electron bridge construction of Z-type heterojunctions to accelerated photogenerated charge transfer for photostability and contaminant mineralization

Advanced oxidation technologies offer new opportunities for pollutant degradation. Despite the existence of numerous photocatalyst heterojunctions for advanced oxidation, their charge transfer and separation efficiency is low due to inadequate interfacial modulation, especially for Type II heterojunctions. Here, through metal reduction, metal defects with regulating the Fermi level and metal electron bridges with facilitate the separation of photo-generated carriers, facilitating the transition from Type II to Z-type heterojunctions. Herein, we designed a Z-Scheme photocatalyst with Bi-based electron bridges (referred to as ‘fishbone-like’ BiVO4/Bi/CuO) synthesized through in situ reduction, utilized for RhB degradation. Under visible light irradiation, the degradation rate of RhB up to 99 % within 120 min, outperforming most previously reported photocatalysts. Notably, the well-designed BiVO4/Bi/CuO exhibits as reaction rate of 4.13 × 10-2 ·min−1, which is 18 times higher than the pure BiVO4. The BiVO4/Bi/CuO photocatalyst demonstrates exceptional stability over 6 reaction cycles spanning 15 h, due to strengthened contact interface of BiVO4/Bi/CuO. The metal Bi can induce the surface plasmon resonance (SPR) effect, enhancing light absorption. Furthermore, Bi-based electron bridges significantly promote the charge transfer across the Z-type heterojunction interface, which were verified by assorted experimental outcomes and density functional theory (DFT) calculations. This work represents a promising platform for the development of highly efficient and stable photocatalysts that have potential in Pollutant degradation applications.

Synergistic Bimetallic Effects of BiSb Anodes Enable Long‐Stable Sodium Storage

AbstractAlloy‐type anodes are of interest for their resource‐rich and high theoretical capacity performance in sodium‐ion batteries (SIBs). However, severe volume expansion may lead to rapid capacity decay and electrode pulverization. In this work, metallic Bi with better structure stability is rationally selected as a skeleton to form a 2D BiSb alloy to alleviate the volume expansion. Interestingly, by combining in‐situ XRD and ex‐situ TEM characterizations, a reversible multi‐step alloying sodium storage mechanism of BiSb ↔ Na(Bi, Sb) ↔ Na3(Bi, Sb) in Bi0.4Sb0.6 anode is elucidated, and the partial amorphization and expanded interlayer spacing of BiSb alloy is also revealed, which greatly alleviate volume expansion thereby enhancing electrochemical stability. Furthermore, density functional theory and kinetic calculations demonstrate that Bi0.4Sb0.6 demonstrates lower Na+ adsorption energy and Na+ diffusion energy barriers, ensuring fast electron and ion transportation during sodium storage. Benefiting from the synergistic effects of binary alloy, Bi0.4Sb0.6 exhibits a high reversible capacity and cycling stability of 446 mAh g−1 at 0.1 A g−1, and 70% high capacity after 1100 cycles at 0.5 A g−1. This work provides new insights and opportunities to develop advanced precise alloy‐type anode materials for SIBs.

Fabrication of interface with capping-bonding synergy to boost CO2 electroreduction to formate

The production of formic acid/formate from electrochemical CO2 reduction reaction (CO2RR) is fascinating but challenging due to the lack of highly active electrocatalysts. Herein, uniform PVP-capped bismuth nanospheres (PVP@Bi-NSs) with a capping-bonding synergy were optimally fabricated to enhance the CO2RR to formate. This study unveils the reaction process in Bi-based solution. It was found that the formation of PVP@Bi-NSs experienced five stages of Bi-O8 (I), Bi-O3 (II), Bi-O4 (III), Bi-Bi6 (IV), and PVP@Bi-NSs (V), corresponding to the nucleation in precursor solution, Bi(OH)3 precipitate, decomposition to KBiO2, reduction to metallic Bi, and PVP coating, respectively. By solvothermal treatment and simply modulating the KOH concentration in the precursor, the hydrophilic ends of PVP molecules can be well bonded to the Bi nanoparticles (Bi-NPs) to form a PVP-capping layer. Compared with the Bi-NPs without PVP coating, this uniform PVP@Bi-NSs displays a higher activity with a maximal Faradaic efficiency (FE) of 92.5 % and part current density (Jformate) of 158.2 mA cm−2 at −0.9 V vs. RHE in the flow cell as well as excellent stability, which is comparable to the state-of-the-art Bi-based catalysts. The maximum Jformate can reach 280 mA cm−2 with an FE of 87.3 % at −1.2 V vs. RHE, meeting the needs of industrial current density. Further characterizations show that the capping effect of PVP contributed to the uniform distribution of nanosized PVP@Bi-NSs, increasing the electrochemical surface areas (ECSAs) and the numbers of CO2RR active sites. The bonding effect of PVP to Bi-NPs enhanced the hydrophobic property of PVP@Bi-NPs, boosting the CO2 absorption and suppressing the hydrogen evolution reaction (HER). DFT calculations reveal that this fabricated structure facilitates the generation of *OCHO intermediate and benefits formate yield. This work provides a fascinating strategy for the design of Bi-based catalysts, enabling interface engineering toward high-efficiency CO2RR.

P-Block-metal bismuth embedded in N/P co-doped carbon nanorods for kinetics-enhanced rechargeable lithium-oxygen batteries

Rechargeable lithium-oxygen batteries (LOBs) are considered one of the most promising electrochemical energy storage devices due to their extremely high theoretical energy density. However, the slow redox kinetics of the oxygen cathode leads to low coulombic efficiency and poor cycling performance, which limits the development of high-performance LOBs. Herein, Bi@NPC heterostructure nanorods are designed with the assistance of p-block metal Bi and successfully synthesized as bifunctional cathode catalysts for LOBs. Experimental and theoretical calculations show that Bi@NPC electrode can significantly reduce overpotential during discharge/charge processes due to the easily tunable localized p-orbitals and resulting versatile electronic structures. Benefiting from p-orbital electrons regulation of Bi atoms, the Bi@NPC electrode exhibited superior specific capacity over 11852.6 mAh g−1, outstanding rate capabilities, and ultralong cycle stability over 83 cycles at 200 mA g−1 with the fixed capacity of 500 mAh g−1. This work reveals an efficient pathway to synthesize p-block metal-based catalysts for high-performance LOBs.

Mn-doped Bi2O3 grown on PTFE-treated carbon paper for electrochemical CO2-to-formate production

BiOx shows promising selectivity in catalyzing the electrochemical reduction of CO2 to formate, but the process suffers from high overpotential and a low rate. Moreover, the active sites are still ambiguous under electrochemical conditions. Herein, we introduce Mn-doping to enhance the activity of binder-free Bi2O3 and elaborate on active sites through in situ Raman and density functional theory (DFT) analyses. The Mn-doped Bi2O3 transforms to Mn-doped Bi2(CO3)O2 in KHCO3 and subsequently reduces to Mn-modified metallic Bi under cathodic potentials. The undoped Bi2O3 is found to follow the same phase transitions but at a different rate. The DFT analyzes the impact of doping the Bi(012) with Mn and indicates significantly improved selectivity for formate generation. Further, the importance of the substrate’s hydrophobicity for long-term stability is demonstrated. This study offers in-depth insights into the design and understanding of doped BiOx-based electrodes for CO2 reduction.

An ultrasensitive free-of-electronic sacrificial agent photoelectrochemical aptasensor for the detection of dibutyl phthalate based on Z-scheme p-n Bi-doped BiOI/Bi2S3 heterojunction

Dibutyl phthalate (DBP), a common and outstanding plasticizer, exhibits estrogenic, mutagenic, carcinogenic, and teratogenic properties. It is easily liberated from plastic materials and pollutes aquatic ecosystems, endangering human health. Therefore, highly sensitive and selective DBP detection methods are necessary. In this work, a free-of-electronic sacrificial agent photoelectrochemical (PEC) aptasensor for DBP detection was constructed using a novel Z-scheme Bi-doped BiOI/Bi2S3 (Bi-BIS) p-n heterojunction. The Bi-BIS composites had higher visible-light absorption, charge transfer, and separation efficiency. This is attributed to the synergistic effect of the formation of Z-scheme p-n heterojunction between BiOI and Bi2S3, the plasma resonance effect of metallic Bi and photosensitization of Bi2S3, thus exhibiting large and stable photocurrent response in the absence of electron sacrificial agent, that was 10.4 and 6.4 times higher than that of BiOI and Bi2S3, respectively. Then, a DBP PEC aptasensor was constructed by modifying the DBP aptamer on the surface of the ITO/Bi-BIS electrode. The aptasensor demonstrated a broad linear range (2–500 pM) and a low detection limit (0.184 pM). What's more, because there is no interference from electronic sacrificial agent, the aptasensor exhibited excellent selectivity in real water samples. Therefore, the proposed PEC has considerable potential for DBP monitoring.

Enhanced X-ray shielding efficiency and visible light degradation performance of a multilayer composite protective material

To mitigate the adverse effects of high-energy radiation, such as X-rays, on patients during medical procedures, a multifunctional composite nanofibrous membrane has been engineered to shield against low-energy X-rays. This study involves integrating processed oil-tea camellia shells (OCS) powder into molten polylactic acid (PLA) for modification. Concurrently, metallic Bi is introduced to enhance Bi2WO6, which is subsequently combined with modified PLA and electrospun into nanofibrous membranes for photocatalytic antimicrobial and organic pollutant degradation. Additionally, sodium hyaluronate (NaHA) and a silver nanoparticle solution are electrospun with PLA to form a skin-friendly protective layer. Following this, a chitosan (CS) solution containing WO3 and B4C is used as a coating on the multilayered membranes. The membranes are then freeze-dried to create sandwich-structured multilayer composite protective material. This method addresses challenges associated with polylactic acid (PLA) in electrospinning and alleviates limitations such as low light absorption and slow charge transfer in Bi2WO6. Compared to similar materials, this composite material is lightweight, flexible for cutting, and exhibits strong X-ray shielding capabilities. The composite nanofibrous membrane demonstrates a shielding efficiency of 97.75 ± 2.05 % at low X-ray energy (46 kVp). Moreover, under visible light, the membrane generates reactive oxygen species, resulting in the efficient removal of 98.03 % of methylene blue (MB), 96.35 % of rhodamine B (Rh.B), and 91.51 % of methyl orange (MO) within 180 minutes. Furthermore, it displays bactericidal activity against E. coli and S. aureus under both dark and light conditions. In natural settings, the composite membrane undergoes gradual degradation in soil, completely decomposing within 28 days due to the influence of rainfall and microorganisms. Consequently, this composite membrane holds significant promise for specialized medical protective applications.

Fermi level limitation in Na1/2Bi1/2TiO3–BaTiO3 piezoceramics by electrochemical reduction of Bi

The (electro)chemical stability of undoped and Zn-doped 0.94Na1/2Bi1/2TiO3–0.06BaTiO3 lead-free piezoceramics (NBT–6BT) was studied. For this purpose, the Fermi level at the interface between NBT–6BT and Sn-doped In2O3 (ITO) electrode is varied by gradually reducing the ITO film either by annealing in vacuum or by applying a voltage across a Pt/NBT–6BT/ITO. The chemical and electronic changes are monitored in situ by x-ray photoelectron spectroscopy. The experiments reveal the formation of metallic Bi when the Fermi level is reaching a value of 2.23 ± 0.10 eV above the valence band maximum, while no reduction of Ti is observed. The electrochemical reduction of Bi constitutes an upper limit of the Fermi level at ≈1 eV below the conduction band minimum. High electron concentrations in the conduction band and a contribution of free electrons to the electrical conductivity of NBT–6BT can, therefore, be excluded. The reduction occurs for an ITO work function of 4.2–4.3 eV. As typical electrode materials such as Ag, Cu, Ni, or Pt have higher work functions, an electrochemical instability of the electrode interfaces in ceramic capacitors is not expected. Under the given experimental conditions (350 °C, electric fields <40 V/mm), no degradation of resistance and no enrichment of Na at the interface are observed.

Preparation of Bi@Ho3+:TiO2/Composite Fiber Photocatalytic Materials and Hydrogen Production via Visible Light Decomposition of Water

Using electrospun nanofibers doped with TiO2 and rare-earth ion Ho3+ as the matrix, and sodium gluconate as the reducing agent, Bi(NO3)3 was reduced using hydrothermal technology to produce Bi@Ho3+:TiO2 composite fiber materials. The materials’ phase, morphology, and photoelectric properties were characterized using various analytical testing methods, including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), and transient photocurrent (IP). During the hydrothermal process, it was confirmed that Bi3+ was reduced by sodium gluconate to form pure Bi nanoparticles, which combined with Ho3+:TiO2 nanofibers to form heterojunctions. By leveraging the surface plasmon resonance (SPR) effect of metallic Bi and the abundant energy level structure and 4f electron transition properties of rare-earth Ho3+, the TiO2 nanofibers underwent dual modification, effectively enhancing the photocatalytic activity and stability of TiO2. Under visible light irradiation, the rate of hydrogen production through water decomposition reached 43.6 μmol·g−1·h−1.

Synergistic integration of metallic Bi and defective TiO2 for enhanced photocatalytic NO removal

The construction of hybrid catalysts is an effective method to enhance catalytic performance, but research on the positioning of the load is limited. In this study, we synthesized two photocatalytic materials by controlling the bismuth-titanium ratio and the site value of Bi modification in the catalyst. The surface-modified photocatalyst, namely 1:0.9 Bi/TiO2, exhibits a photocatalytic efficiency of 68.9 % for the abatement of ppb-level NO in the presence of visible irradiation. This efficiency was significantly superior to that of the corresponding one-step synthesized Bi/TiO2 (48.7 %) and the TiO2 (18.6 %). Furthermore, it promotes nitrate formation and suppresses the generation of toxic NO2. Capture experiments indicate that the same active species are involved in both surface-loaded and uniformly loaded catalysts. The differences in their performance can be attributed to the higher vacancy concentration in the surface-loaded catalysts and the different local coordination environments of vacancies in the catalysts, altering the adsorption capability of oxygen molecules. This work offers fresh perspectives for the generation of efficient photocatalysts.

Unraveling the effect of anions (molybdate and carbonate) on reconstruction of BiOX catalysts for electrocatalytic CO2 to formate

The catalytic performance of Bi2MoO6 and Bi2O2CO3, synthesized through the ion-exchange of Bi2MoO6 with CO32–, was investigated to discern the influence of anions on the electrochemical CO2 reduction reactions (ECO2RR) activity. In-situ Raman measurements uncovered that the reconstruction of Bi2MoO6 proceeded rapidly reduction to metallic Bi after reduction onset, marked by a short-lived transition state, while the Bi2O2CO3 structure remained intact. The anion effects on the reconstruction were attributed to their influence on Bi-O bonding energy, with the Bi-O bond in Bi-O-C being stronger due to higher electronegativity of carbon than Bi, which enhances electron transfer from Bi to O; conversely, the similarity in electronegativity between Mo and Bi weakened the Bi-O bond. This thesis is also applicable for predicting the reconstruction of Bi2WO6 and BiOI samples through electrolysis. The catalytic activity was correlated with the structural changes. Bi2O2CO3 demonstrated a peak formate selectivity of 93.4 % at a current density of 36.2 mA cm−2 at −1.0 V versus the reversible hydrogen electrode (RHE). Additionally, a high FEformate of over 90 % with a jformate of 554.8 mA cm−2 was obtained in the flow cell. At a comparable potential of −1.0 V versus RHE, Bi2MoO6 showed a formate Faradaic efficiencies of 67.4 % at a current density of 26.1 mA cm−2. DFT calculations revealed that the retention of Bi3+ in Bi2O2CO3 is more catalytically active for *OCHO formation than the metallic Bi produced from Bi2MoO6. This suggests that anions in BiOX can modulate ECO2RR performance by governing the reconstruction of pre-catalysts. This study provides a pathway for the rational design of electrocatalysts for liquid fuel synthesis.

Effect of laser power density on formation of oxide particles during ablation of metallic bismuth in atmospheric air

Purposeful synthesis of bismuth oxide nanoparticles (NPs) of various crystal modifications is important for biomedicine, photocatalysis and other applications. In this work, pulsed laser ablation of a metallic Bi target in atmospheric air is used to obtain β-Bi2O3 NPs. The effect of the Nd:YAG laser radiation power density (1064 nm, 7 ns) in the range of 0.1–1.2 GW/cm2 on the features of formation of NPs under nonequilibrium conditions is studied, for which the spectra of laser-induced plasma are recorded and analyzed, the plasma composition is determined, and the temperature of the plasma plume is estimated. The NPs are comprehensively characterized using TEM, XRD, FTIR, Raman, and UV–Vis spectroscopies, and electrophoretic light scattering, which make it possible to determine their morphology, crystal structure, chemical composition, and optical properties. The photocatalytic activity of the resulting nanopowders in the Rhodamine B dye decomposition reaction is assessed.