Enhancing Hydrogen Storage Capacity of Pd Nanoparticles by Sandwiching between Inorganic Nanosheets

H₂ is regarded to play a crucial role in the transition from a fossil fuel-based energy economy towards an environmentally friendly one. However, storage of H₂ is still challenging, but palladium (Pd) based materials show exciting properties. Therefore, nanoparticulate Pd has been intensely studied for hydrogen storage in the past years. Here, we stabilize Pd nanoparticles by intercalation between inorganic nanosheets of hectorite (NaHec). Compared to nanoparticles stabilized by the polymer polyvinylpyrrolidone (PVP), the H₂ storage capacity was found to be 86 % higher for identical Pd nanoparticles being intercalated between nanosheets. We attribute this remarkably enhanced H₂ storage capacity to the partial oxidation of Pd, as evidenced by X-ray photoelectron spectroscopy (XPS). The higher amount of holes in the 4d band leads to a higher amount of H₂ that can be absorbed when Pd is stabilized between the nanosheets of hectorite compared to the PVP stabilized nanoparticles

Ni@onion-like carbon and Co@amorphous carbon: control of carbon structures by metal ion species in MOFs

We first report the facile synthesis of metal-carbon composites consisting of metal nanoparticles (NPs) and different types of carbon species: onion-like and amorphous carbon, Ni@onion-like carbon and Co@amorphous carbon. By simply changing the metal species in an isostructural metal-organic framework, thermal decompositions of MOF-74 directly afforded different types of metal NPs and carbon composites, which exhibited good electrical conductivity. In particular, the Ni@onion-like carbon, having a well-ordered carbon structure, had high electrical conductivity (sigma = 5.3 omega(-1) cm(-1) at 295 K), explained by a modified model of the Efros-Shklovskii variable range hopping

Crystal Structure Control of Binary and Ternary Solid-Solution Alloy Nanoparticles with a Face-Centered Cubic or Hexagonal Close-Packed Phase

The crystal structure significantly affects the physical and chemical properties of solids. However, the crystal structure-dependent properties of alloys are rarely studied because controlling the crystal structure of an alloy at the same composition is extremely difficult. Here, for the first time, we successfully demonstrate the synthesis of binary Ru–Pt (Ru/Pt = 7:3) and Ru–Ir (Ru/Ir = 7:3) and ternary Ru–Ir–Pt (Ru/Ir/Pt = 7:1.5:1.5) solid-solution alloy nanoparticles (NPs) with well-controlled hexagonal close-packed (hcp) and face-centered cubic (fcc) phases, through the chemical reduction method. The crystal structure control is realized by precisely tunning the reduction speeds of the metal precursors. The effect of the crystal structure on the catalytic performance of solid-solution alloy NPs is systematically investigated. Impressively, all the hcp alloy NPs show superior electrocatalytic activities for the hydrogen evolution reaction in alkaline solution compared with the fcc alloy NPs. In particular, hcp-RuIrPt exhibits extremely high intrinsic (mass) activity, which is 3.1 (3.2) and 6.7 (6.9) times enhanced compared to that of fcc-RuIrPt and commercial Pt/C

Efficient overall water splitting in acid with anisotropic metal nanosheets

超高効率な水の電気分解を実現するナノシート状合金触媒を開発 --再生可能エネルギーによる水素社会実現へ大きく貢献--. 京都大学プレスリリース. 2021-02-17.Water is the only available fossil-free source of hydrogen. Splitting water electrochemically is among the most used techniques, however, it accounts for only 4% of global hydrogen production. One of the reasons is the high cost and low performance of catalysts promoting the oxygen evolution reaction (OER). Here, we report a highly efficient catalyst in acid, that is, solid-solution Ru‒Ir nanosized-coral (RuIr-NC) consisting of 3 nm-thick sheets with only 6 at.% Ir. Among OER catalysts, RuIr-NC shows the highest intrinsic activity and stability. A home-made overall water splitting cell using RuIr-NC as both electrodes can reach 10 mA cm−2geo at 1.485 V for 120 h without noticeable degradation, which outperforms known cells. Operando spectroscopy and atomic-resolution electron microscopy indicate that the high-performance results from the ability of the preferentially exposed {0001} facets to resist the formation of dissolvable metal oxides and to transform ephemeral Ru into a long-lived catalyst

Phase Control of Solid-Solution Nanoparticles beyond the Phase Diagram for Enhanced Catalytic Properties

The crystal structure, which intrinsically affects the properties of solids, is determined by the constituent elements and composition of solids. Therefore, it cannot be easily controlled beyond the phase diagram because of thermodynamic limitations. Here, we demonstrate the first example of controlling the crystal structures of a solid-solution nanoparticle (NP) entirely without changing its composition and size. We synthesized face-centered cubic (fcc) or hexagonal close-packed (hcp) structured PdxRu₁–x NPs (x = 0.4, 0.5, and 0.6), although they cannot be synthesized as bulk materials. Crystal-structure control greatly improves the catalytic properties; that is, the hcp-PdxRu₁–x NPs exceed their fcc counterparts toward the oxygen evolution reaction (OER) in corrosive acid. These NPs only require an overpotential (η) of 200 mV at 10 mA cm⁻², can maintain the activity for more than 20 h, greatly outperforming the fcc-Pd₀.₄Ru₀.₆ NPs (η = 280 mV, 9 min), and are among the most efficient OER catalysts reported. Synchrotron X-ray-based spectroscopy, atomic-resolution electron microscopy, and density functional theory (DFT) calculations suggest that the enhanced OER performance of hcp-PdRu originates from the high stability against oxidative dissolution

Localized thermal levering events drive spontaneous kinetic oscillations during CO oxidation on Rh/Al 2 O 3

Unravelling kinetic oscillations, which arise spontaneously during catalysis, has been a challenge for decades but is important not only to understand these complex phenomena but also to achieve increased activity. Here we show, through temporally and spatially resolved operando analysis, that CO oxidation over Rh/Al2O3 involves a series of thermal levering events—CO oxidation, Boudouard reaction and carbon combustion—that drive oscillatory CO2 formation. This catalytic sequence relies on harnessing localized temperature episodes at the nanoparticle level as an efficient means to drive reactions in situations in which the macroscopic conditions are unfavourable for catalysis. This insight provides a new basis for coupling thermal events at the nanoscale for efficient harvesting of energy and enhanced catalyst technologies

Localized thermal levering events drive spontaneous kinetic oscillations during CO oxidation on Rh/Al2O3

Unravelling kinetic oscillations, which arise spontaneously during catalysis, has been a challenge for decades but is important not only to understand these complex phenomena but also to achieve increased activity. Here we show, through temporally and spatially resolved operando analysis, that CO oxidation over Rh/Al2O3 involves a series of thermal levering events—CO oxidation, Boudouard reaction and carbon combustion—that drive oscillatory CO2 formation. This catalytic sequence relies on harnessing localized temperature episodes at the nanoparticle level as an efficient means to drive reactions in situations in which the macroscopic conditions are unfavourable for catalysis. This insight provides a new basis for coupling thermal events at the nanoscale for efficient harvesting of energy and enhanced catalyst technologies