Nanoalloys (NAs) have extraordinary catalytic properties, but metals are often immiscible giving compositional limits on catalytic design. It is generally believed that solution‐based chemical synthesis is inadequate for obtaining NAs, and often exotic shock synthesis or severe decomposition or reduction reactions are required. However, such methods only work on the laboratory scale making real‐world applications difficult. Here, a general solvothermal method is reported to obtain phase‐pure bimetallic and high‐entropy nano‐alloys across the entire composition range. Tuning of solvent chemistry and precursors leads to six different bimetallic NAs: PdxRu1‐x, PtxRu1‐x, IrxRu1‐x, RhxRu1‐x, Ir1‐xPtx, and Rh1‐xPtx, without immiscibility regions. All samples have face‐centered‐cubic crystal structures, which have not previously been observed for the ruthenium‐based systems. Additionally, quaternary and quinary systems are produced, demonstrating the ability to obtain medium‐ and high‐entropy NAs. The method described herein provides a simple, general production method of previously unknown solid solutions throughout their entire composition range potentially allowing for detailed tuning of nanocatalyst properties.
The concept of secondary building units (SBUs) is central to all science on metal‐organic frameworks (MOFs), and they are widely used to design new MOF materials. However, the presence of SBUs during MOF formation remains controversial, and the formation mechanism of MOFs remains unclear, due to limited information about the evolution of prenucleation cluster structures. Here in situ pair distribution function (PDF) analysis was used to probe UiO‐66 formation under solvothermal conditions. The expected SBU—a hexanuclear zirconium cluster—is present in the metal salt precursor solution. Addition of organic ligands results in a disordered structure with correlations up to 23 Å, resembling crystalline UiO‐66. Heating leads to fast cluster aggregation, and further growth and ordering results in the crystalline product. Thus, SBUs are present already at room temperature and act as building blocks for MOF formation. The proposed formation steps provide insight for further development of MOF synthesis.
High-entropy alloy (HEA) nanoparticles hold great promise as tunable catalysts. Despite the fact that alloy formation is typically difficult in oxygen-rich environments, we found that Pt-Ir-Pd-Rh-Ru nanoparticles can be synthesized under benign low-temperature solvothermal conditions. In situ X-ray scattering and transmission electron microscopy reveal the solvothermal formation mechanism of Pt-Ir-Pd-Rh-Ru nanoparticles. For the individual metal acetylacetonate precursors, formation of single metal nanoparticles takes place at temperatures spanning from ca. 150 8C for Pd to ca. 350 8C for Ir. However, for the mixture, homogenous Pt-Ir-Pd-Rh-Ru HEA nanoparticles can be obtained around 200 8C due to autocatalyzed metal reduction at the (111) facets of the forming crystallites. The autocatalytic formation mechanism suggests that many types of HEA nanocatalysts should accessible with scalable solvothermal reactions, thereby providing broad availability and tunability.
High-entropy alloy (HEA) nanoparticles hold great promise as tunable catalysts. Despite the fact that alloy formation is typically difficult in oxygen-rich environments, we found that Pt-Ir-Pd-Rh-Ru nanoparticles can be synthesized under benign low-temperature solvothermal conditions. In situ X-ray scattering and transmission electron microscopy reveal the solvothermal formation mechanism of Pt-Ir-Pd-Rh-Ru nanoparticles. For the individual metal acetylacetonate precursors, formation of single metal nanoparticles takes place at temperatures spanning from ca. 150 8C for Pd to ca. 350 8C for Ir. However, for the mixture, homogenous Pt-Ir-Pd-Rh-Ru HEA nanoparticles can be obtained around 200 8C due to autocatalyzed metal reduction at the (111) facets of the forming crystallites. The autocatalytic formation mechanism suggests that many types of HEA nanocatalysts should accessible with scalable solvothermal reactions, thereby providing broad availability and tunability.
The application of thermoelectrics for energy harvesting depends strongly on operational reliability and it is therefore desirable to investigate the structural integrity of materials under operating conditions. We have developed an operando setup capable of simultaneously measuring X-ray scattering data and electrical resistance on pellets subjected to electrical current. Here, operando investigations of β-Zn4Sb3 are reported at current densities of 0.5, 1.14 and 2.3 A mm−2. At 0.5 A mm−2 no sample decomposition is observed, but Rietveld refinements reveal increased zinc occupancy from the anode to the cathode demonstrating zinc migration under applied current. At 1.14 A mm−2 β-Zn4Sb3 decomposes into ZnSb, but pair distribution function analysis shows that Zn2Sb2 units are preserved during the decomposition. This identifies the mobile zinc in β-Zn4Sb3 as the linkers between the Zn2Sb2 units. At 2.3 A mm−2 severe Joule heating triggers transition into the γ-Zn4Sb3 phase, which eventually decomposes into ZnSb, demonstrating Zn ion mobility also in γ-Zn4Sb3 under electrical current.
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