Thermoelectric properties of (Bi0.25Sb0.75)2Te3 alloys fabricated by hot-pressing method

Thermoelectric properties of the hot-pressed p-type (Bi_0.25Sb_0.75)₂Te₃ alloy were characterized with variation of the hot-pressing temperature and the starting powder size. The roles of the factors which affect the Seebeck coefficient of the hot-pressed (Bi_0.25Sb_0.75)₂Te₃ alloy has been elucidated in this study. The donor-like behavior of oxygen could be one of the possible explanations for the higher Seebeck coefficient of the hot-pressed (Bi_0.25Sb_0.75)₂Te₃ alloy. Te vacancies formed by mechanical deformation during the powdering process significantly promote the diffusion of second phase Te atoms into their lattice sites so that the matrix Te solubility approaches its equilibrium value at a given temperature in a relatively short length of time. Using the Seebeck coefficient at various hot-pressing temperatures, the micro-phase diagram near the stoichiometric composition of (Bi_0.25Sb_0.75)₂Te₃ was evaluated.     

Solvothermal synthesis of Bi2Te3 nanotubes by the interdiffusion of Bi and Te metals

Bi₂Te₃ nanotubes with a one-dimensional structure have been synthesized by a solvothermal method using Te nanowires and Bi metals formed by the liquid phase reduction of Bi³⁺. The alloying between Bi and Te was formed by the diffusion process through an interface of two joined metals. The void formed in the diffusion process induced the formation of binary-nanotubes from the single-component nanowires. The microstructures of the Te nanowires, such as its particle morphology and crystal density, were a function of the temperature and had considerable influence on the alloying into Bi₂Te₃ nanotubes. When the reduction rate from Bi³⁺ to Bi is constant, the alloying between Bi and Te metals was affected by the rate of diffusion of the Te atoms. The aggregation of the Te nanowires and diffusion resistance caused by the cross packed crystal structure of the Te nanowires disrupted migration of Te atoms from the inside of the Te nanowire.     

Interface-Induced Electrocatalytic Enhancement of CO2-to-Formate Conversion on Heterostructured Bismuth-Based Catalysts

Electrochemical CO₂ reduction reaction (CO₂RR) is a promising approach to convert CO₂ to carbon-neutral fuels using external electric powers. Here, the Bi₂S₃-Bi₂O₃ nanosheets possessing substantial interface being exposed between the connection of Bi₂S₃ and Bi₂O₃ are prepared and subsequently demonstrate to improve CO₂RR performance. The electrocatalyst shows formate Faradaic efficiency (FE) of over 90% in a wide potential window. A high partial current density of about 200 mA cm^?2 at ?1.1 V and an ultralow onset potential with formate FE of 90% are achieved in a flow cell. The excellent electrocatalytic activity is attributed to the fast-interfacial charge transfer induced by the electronic interaction at the interface, the increased number of active sites, and the improved CO₂ adsorption ability. These collectively contribute to the faster reaction kinetics and improved selectivity and consequently, guarantee the superb CO₂RR performance. This study provides an appealing strategy for the rational design of electrocatalysts to enhance catalytic performance by improving the charge transfer ability through constructing a functional heterostructure, which enables interface engineering toward more efficient CO₂RR.     

Highly Selective N2 Electroreduction to NH3 Using a Boron-Vacancy-Rich Diatomic Nb?B Catalyst

The ambient electrochemical N₂ reduction reaction (NRR) is a future approach for the artificial NH₃ synthesis to overcome the problems of high-energy consumption and environmental pollution by Haber–Bosch technology. However, the challenge of N₂ activation on a catalyst surface and the competitive hydrogen evolution reaction make the current NRR unsatisfied. Herein, this work demonstrates that NbB₂ nanoflakes (NFs) exhibit excellent selectivity and durability in NRR, which produces NH₃ with a production rate of 30.5 µg h⁻¹ mg_cat⁻¹ and a super-high Faraday efficiency (FE) of 40.2%. The high-selective NH₃ production is attributed to the large amount of active B vacancies on the surface of NbB₂ NFs. Density functional theory calculations suggest that the multiple atomic adsorption of N₂ on both unsaturated Nb and B atoms results in a significantly stretched N₂ molecule. The weakened NN triple bonds are easier to be broken for a biased NH₃ production. The diatomic catalysis is a future approach for NRR as it shows a special N₂ adsorption mode that can be well engineered.     

Effects of excess Te on the thermoelectric properties of p-type 25% Bi2Te3-75% Sb2Te3 single crystal and hot-pressed sinter

Effects of excess Te on the thermoelectric properties of p-type 25% Bi₂Te₃-75% Sb₂Te₃ single crystal and hot-pressed sinter were characterized and understood with the micro-phase diagram near the stoichiometric composition obtained by measuring the equilibrium Seebeck coefficient. Thermoelectric properties of the 25% Bi₂Te₃-75% Sb₂Te₃ single crystal were varied with the amount of excess Te, as -phase of the single crystal becomes less Te-deficient with adding more excess Te. However, thermoelectric properties of the hot-pressed sinter were not varied with the amount of excess Te, because the composition of -phase is not changed with the amount of excess Te. While a maximum figure-of-merit of 2.39 × 10^–3/K at 300 K was obtained for the 25% Bi₂Te₃-75% Sb₂Te₃ single crystal by adding 6 wt % excess Te, the hot-pressed 25% Bi₂Te₃-75% Sb₂Te₃ sinter exhibited the figure-of-merit of 2.97 × 10^–3/K regardless of the excess Te amount.     

Selective CO2 Electroreduction to Formate on Polypyrrole-Modified Oxygen Vacancy-Rich Bi2O3 Nanosheet Precatalysts by Local Microenvironment Modulation

Challenges remain in the development of highly efficient catalysts for selective electrochemical transformation of carbon dioxide (CO₂) to high-valued hydrocarbons. In this study, oxygen vacancy-rich Bi₂O₃ nanosheets coated with polypyrrole (Bi₂O₃@PPy NSs) are designed and synthesized, as precatalysts for selective electrocatalytic CO₂reduction to formate. Systematic material characterization demonstrated that Bi₂O₃@PPy precatalyst can evolve intoBi₂O₂CO₃@PPy nanosheets with rich oxygen vacancies (Bi₂O₂CO₃@PPy NSs) via electrolyte-mediated conversion and function as the real active catalyst for CO₂ reduction reaction electrocatalysis. Coating catalyst with a PPy shell can modulate the interfacial microenvironment of active sites, which work in coordination with rich oxygen vacancies in Bi₂O₂CO₃ and efficiently mediate directional selective CO₂ reduction toward formate formation. With the fine-tuning of interfacial microenvironment, the optimized Bi₂O₃@PPy-2 NSs derived Bi₂O₂CO₃@PPy-2 NSs exhibit a maximum Faradaic efficiency of 95.8% at −0.8 V (versus. reversible hydrogen electrode) for formate production. This work might shed some light on designing advanced catalysts toward selective electrocatalytic CO₂ reduction through local microenvironment engineering.     

Porous and Partially Dehydrogenated Fe2+-Containing Iron Oxyhydroxide Nanosheets for Efficient Electrochemical Nitrogen Reduction Reaction (ENRR)

The design and development of efficient catalysts for electrochemical nitrogen reduction reaction (ENRR) under ambient conditions are critical for the alternative ammonia (NH₃) synthesis from N₂ and H₂O, wherein iron-based electrocatalysts exhibit outstanding NH₃ formation rate and Faradaic efficiency (FE). Here, the synthesis of porous and positively charged iron oxyhydroxide nanosheets by using layered ferrous hydroxide as a starting precursor, which undergoes topochemical oxidation, partial dehydrogenated reaction, and final delamination, is reported. As the electrocatalyst of ENRR, the obtained nanosheets with a monolayer thickness and 10-nm mesopores display exceptional NH₃ yield rate (28.5 µg h⁻¹ mg_cat.⁻¹) and FE (13.2%) at a potential of −0.4 V versus RHE in a phosphate buffered saline (PBS) electrolyte. The values are much higher than those of the undelaminated bulk iron oxyhydroxide. The larger specific surface area and positive charge of the nanosheets are beneficial for providing more exposed reactive sites as well as retarding hydrogen evolution reaction. This study highlights the rational control on the electronic structure and morphology of porous iron oxyhydroxide nanosheets, expanding the scope of developing non-precious iron-based highly efficient ENRR electrocatalysts.     

Physical properties of Bi2 (Te,Se)3 and Bi2Se1.2Te1.8 prepared using solid-state microwave synthesis

Bi₂(Te, Se)₃ and Bi₂Se_1.2Te_1.8 bulk products were synthesised using standard solid-state microwave synthesis. The Bi₂(Te, Se)₃ and Bi₂Se_1.2Te_1.8 were then deposited thermally onto glass substrates at a pressure of 10^? 6 Torr. The structure of the samples was analysed using X-ray diffraction (XRD), and the powders and thin films were observed to be polycrystalline and rhombohedral in structure. The surface morphology of the samples was determined using scanning electron microscopy (SEM). From the measurements of optical properties, the energy gap values for the Bi₂Te₃, Bi₂Se₃, and Bi₂Se_1.2Te_1.8 thin films were 0.43, 0.73, and 0.65 eV, respectively.     

Facile synthesis and thermoelectric studies of n-type bismuth telluride nanorods with cathodic stripping Te electrode

Bismuth telluride (Bi₂Te₃) nanorods (NRs) of n-type thermoelectric materials were prepared using an electrogenerated precursor of tellurium electrode in the presence of Bi³⁺ and mercapto protecting agent in aqueous solution under atmosphere condition. The optimal preparation conditions were obtained with ratio of Bi³⁺ to mercapto group and Te coulomb by photoluminescence spectra. The mechanism for generation of Bi₂Te₃ precursor was investigated via the cyclic voltammetry. The highly crystalline rhombohedral structure of as-prepared Bi₂Te₃ NRs with the shell of Bi₂S₃ was evaluated with high resolution transmission electron microscopy (HRTEM) and powder X-ray diffraction (XRD) spectroscopy. The near-infrared absorption of synthetic Bi₂Te₃ NRs was characterized with spectrophotometer to obtain information of electron at interband transition. The thermoelectric performance of Bi₂Te₃ NRs was assessed with the result of electrical resistivity, Seebeck coefficient, thermal conductivity, and the figure of merit ZT parameters, indicating that thermoelectric performance of as-prepared Bi₂Te₃ nanocrystals was improved by reducing thermal conductivity while maintaining the power factor.     

P-Block Metal-Based Electrocatalysts for Nitrogen Reduction to Ammonia: A Minireview

Electrochemical nitrogen reduction reaction (NRR) to ammonia (NH₃) using renewable electricity provides a promising approach towards carbon neutral. What's more, it has been regarded as the most promising alternative to the traditional Haber-Bosch route in current context of developing sustainable technologies. The development of a class of highly efficient electrocatalysts with high selectivity and stability is the key to electrochemical NRR. Among them, P-block metal-based electrocatalysts have significant application potential in NRR for which possessing a strong interaction with the N 2p orbitals. Thus, it offers a good selectivity for NRR to NH₃. The density of state (DOS) near the Fermi level is concentrated for the P-block metal-based catalysts, indicating the ability of P-block metal as active sites for N₂ adsorption and activation by donating p electrons. In this work, we systematically review the recent progress of P-block metal-based electrocatalysts for electrochemical NRR. The effect of P-block metal-based electrocatalysts on the NRR activity, selectivity and stability are discussed. Specifically, the catalyst design, the nature of the active sites of electrocatalysts and some strategies for boosting NRR performance, the reaction mechanism, and the impact of operating conditions are unveiled. Finally, some challenges and outlooks using P-block metal-based electrocatalysts are proposed.     

Structural and thermoelectric characterizations of high pressure sintered nanocrystalline Bi2Te3 bulks

Using Bi₂Te₃ nanopowders prepared from ball milling of elemental Bi and Te, nanocrystalline Bi₂Te₃ bulks were fabricated with high pressure sintering technique under variable pressures. The structural and thermoelectric properties were characterized, revealing a strong correlation with the sintering pressure. The nanocrystalline Bi₂Te₃ bulk fabricated under 2 GPa exhibits good thermoelectric properties with ZT over 0.8 from 300 to 460 K and a peak ZT of 1.03 occurring at 403 K, which can be attributed to the small thermal conductivity from enhanced phonon scattering by grain boundaries and defects, as well as to the good electrical property comparable to that of the zone melting material.     

Self-intercalation in Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>〈Cu〉

We have studied the electronic properties of Bi₂Te₃〈Cu〉 crystals. The results indicate that, during natural growth and subsequent self-intercalation, copper layers are formed between Te(I)-Te(I) layers in the basal plane (0001). On cleaved (0001) surfaces, quasi-two-dimensional layers with islands were found. Studies of Shubnikov-de Haas-like 4.2-K magnetoresistance oscillations in Bi₂Te₃〈Cu〉 revealed additional series of oscillations for H ⊥ C ⊥ I. We observed magnetoresistance oscillations at temperatures from 240 to 280 K, due to the magnetophonon resonance. The magnetophonon oscillations in self-intercalated Bi₂Te₃〈Cu〉 are periodic and better defined in comparison with copper-intercalated Bi₂Te₃.     

AuCu Alloy Nanoparticle Embedded Cu Submicrocone Arrays for Selective Conversion of CO2 to Ethanol

The CO₂ reduction reaction (CO₂RR) driven by renewable electricity represents a promising strategy toward alleviating the energy shortage and environmental crisis facing humankind. Cu species, as one type of versatile electrocatalyst for the CO₂RR, attract tremendous research interest. However, for C₂ products, ethanol formation is commonly less favored over Cu electrocatalysts. Herein, AuCu alloy nanoparticle embedded Cu submicrocone arrays (AuCu/Cu‐SCA) are constructed as an active, selective, and robust electrocatalyst for the CO₂RR. Enhanced selectivity for EtOH is gained, whose Faradaic efficiency (FE) reaches 29 ± 4%, while ethylene formation is relatively inhibited (16 ± 4%) in KHCO₃ aqueous solution. The ratio between partial current densities of EtOH and C₂H₄ (j_EtOH/j_C2H4) can be tuned in the range from 0.15 ± 0.27 to 1.81 ± 0.55 by varying the Au content of the electrocatalysts. The combined experimental and theoretical calculation results identify the importance of Au in modifying binding energies of key intermediates, such as CH₂CHO*, CH₃CHO*, and CH₃CH₂O*, which consequently modify the activity and selectivity (j_EtOH/j_C2H4) for the CO₂RR. Moreover, AuCu/Cu‐SCA also shows high durability with both the current density and FE_EtOH being largely maintained for 24 h electrocatalysis.     

A Generalized Surface Chalcogenation Strategy for Boosting the Electrochemical N2 Fixation of Metal Nanocrystals

Electrocatalytic nitrogen reduction reaction (NRR) is a promising process relative to energy-intensive Haber–Bosch process. While conventional electrocatalysts underperform with sluggish paths, achieving dissociation of N₂ brings the key challenge for enhancing NRR. This study proposes an effective surface chalcogenation strategy to improve the NRR performance of pristine metal nanocrystals (NCs). Surprisingly, the NH₃ yield and Faraday efficiency (FE) (175.6 ± 23.6 mg h^–1 g^–1_Rh and 13.3 ± 0.4%) of Rh-Se NCs is significantly enhanced by 16 and 15 times, respectively. Detailed investigations show that the superior activity and high FE are attributed to the effect of surface chalcogenation, which not only can decrease the apparent activation energy, but also inhibit the occurrence of the hydrogen evolution reaction (HER) process. Theoretical calculations reveal that the strong interface strain effect within core@shell system induces a critical redox inversion, resulting in a rather low valence state of Rh and Se surface sites. Such strong correlation indicates an efficient electron-transfer minimizing NRR barrier. Significantly, the surface chalcogenation strategy is general, which can extend to create other NRR metal electrocatalysts with enhanced performance. This strategy open a new avenue for future NH₃ production for breakthrough in the bottleneck of NRR.     

X-ray diffraction study of Ge-Bi-Te mixed-layer ternary compounds

The structures of the Ge₃Bi₂Te₆, GeBi₆Te₁₀, and Ge₂Bi₁₀Te₁₇ compounds, belonging to thenGeTe ·mBi₂Te₃ homologous series, were studied by x-ray diffraction. For Ge₃Bi₂Te₆, the atomic coordinates, lattice parameters, and interatomic distances were determined. This compound was shown to contain mixed (Ge + Bi) cation layers. The c parameters of the hexagonal cells of GeBi₆Te₁₀ and Ge₂Bi₁₀Te₁₇ were determined. It is shown that the x-ray patterns from the cleaved surfaces of single-crystalnGeTe ·mBi₂Te₃ compounds vary in a systematic manner with increasingn/m ratio, which is attributable to the filling of empty Te octahedra. For 00l reflections, indexl can be expressed in general form throughn andm.     

Interfacially Engineered Nanoporous Cu/MnOx Hybrids for Highly Efficient Electrochemical Ammonia Synthesis via Nitrate Reduction

Electrochemical reduction of nitrate to ammonia (NH₃) not only offers a promising strategy for green NH₃ synthesis, but also addresses the environmental issues and balances the perturbed nitrogen cycle. However, current electrocatalytic nitrate reduction processes are still inefficient due to the lack of effective electrocatalysts. Here 3D nanoporous Cu/MnO_x hybrids are reported as efficient and durable electrocatalysts for nitrate reduction reaction, achieving the NH₃ yield rates of 5.53 and 29.3 mg h⁻¹ mg_cat.⁻¹ with 98.2% and 86.2% Faradic efficiency in 0.1 m Na₂SO₄ solution with 10 and 100 mm KNO₃, respectively, which are higher than those obtained for most of the reported catalysts under similar conditions. Both the experimental results and density functional theory calculations reveal that the interface effect between Cu/MnO_x interface could reduce the free energy of rate determining step and suppress the hydrogen evolution reaction, leading to the enhanced catalytic activity and selectivity. This work provides an approach to design advanced materials for NH₃ production via electrochemical nitrate reduction.     

A General Strategy to Glassy M-Te (M = Ru,Rh, Ir) Porous Nanorods for Efficient Electrochemical N2 Fixation

Electrochemical conversion of nitrogen (N₂) into value-added ammonia (NH₃) is highly desirable yet formidably challenging due to the extreme inertness of the N₂ molecule, which makes the development of a robust electrocatalyst prerequisite. Herein, a new class of bullet-like M-Te (M = Ru, Rh, Ir) glassy porous nanorods (PNRs) is reported as excellent electrocatalysts for N₂ reduction reaction (NRR). The optimized IrTe₄ PNRs present superior activity with the highest NH₃ yield rate (51.1 µg h⁻¹ mg⁻¹_cat.) and Faraday efficiency (15.3%), as well as long-term stability of up to 20 consecutive cycles, making them among the most active NRR electrocatalysts reported to date. Both the N₂ temperature-programmed desorption and valence band X-ray photoelectron spectroscopy data show that the strong chemical adsorption of N₂ is the key for enhancing the NRR and suppressing the hydrogen evolution reaction of IrTe₄ PNRs. Density functional theory calculations comprehensively identify that the superior adsorption strength of IrTe₄ adsorptions originates from the synergistic collaboration between electron-rich Ir and the highly electroactive surrounding Te atoms. The optimal adsorption of both N₂ and H₂O in alkaline media guarantees the superior consecutive NRR process. This work opens a new avenue for designing high-performance NRR electrocatalysts based on glassy materials.     

Ag_2Te掺杂对p型Bi_(0.5)Sb_(1.5)Te_3块状合金热电性能的影响

采用真空熔炼、机械球磨及放电等离子烧结技术(SPS)制备得到了(Ag2Te)x(Bi0.5Sb1.5Te3)1-x(x=0,0.025,0.05,0.1)系列样品,性能测试表明,Ag2Te的掺入可以显著改变材料的热电性能变化趋势,掺杂样品在温度为450~550K范围内具有较未掺杂样品更优的热电性能.适当量的Ag2Te掺入能够有效地提高材料的声子散射,降低材料的热导率.在测试温度范围内,(Ag2Te)0.05(Bi0.5Sb1.5Te3)0.95具有最低的晶格热导,室温至575K范围内保持在0.2~0.3W/(m·K)之间,在575K时,(Ag2Te)0.05(Bi0.5Sb1.5Te3)0.95试样具有最大热电优值ZT=0.84,相较于未掺杂样品提高了约20%.     

Bi,Te, and Bi-Te nanoparticles in opal matrices

Bi, Te, and Bi₂Te₃ nanoparticles have been prepared by reducing bismuth salts, telluric acid, and their decomposition products with supercritical isopropanol in opal pores.