Controlled Loading of Small Aun Clusters (n = 10–39) onto BaLa4Ti4O15 Photocatalysts: Toward an Understanding of Size Effect of Cocatalyst on Water-Splitting Photocatalytic Activity

Negishi, Yuichi; Matsuura, Yoshiki; Tomizawa, Ryota; Kurashige, Wataru; Niihori, Yoshiki; Takayama, Tomoaki; Iwase, Akihide; Kudo, Akihiko

doi:10.1021/jp5122432

Cited by 90 publications

(107 citation statements)

References 53 publications

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“…For ease of presentation, a generic form of [M n (SR) m ] q /support or M n /support is adopted hereafter to refer to supported ligand‐on [M n (SR) m ] q or ligand‐off M n NCs, respectively. Similar reverse size‐dependent catalytic activity has also been observed in many other reactions catalyzed by thiolate‐protected Au NCs, including oxidization of methyl phenyl sulfide, electroreduction of O 2 , photocatalytic decomposition of methyl viologen, and water splitting reactions . A notable exception of such descending trend was reported by Liu et al (Figure b) .…”

Section: Catalytic and Biomedical Applications Of Metal Nanoclusterssupporting

confidence: 80%

Engineering Functional Metal Materials at the Atomic Level

et al. 2018

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With continuous research efforts devoted into synthesis and characterization chemistry of functional nanomaterials in the past decades, the development of metal materials is stepping into a new era, where atom-by-atom customization of property-dictating structural attributes is expected. Herein, the state-of-the-art modulation of functional metal nanomaterials at the atomic level, by size- and structure-controlled synthesis of thiolate-protected metal (e.g., Au and Ag) nanoclusters (NCs), is exemplified. Metal NCs are ultrasmall (<3 nm) particles with hierarchical primary, secondary, and tertiary structures, reminiscent of natural proteins or enzymes. Given the proven dependence of their physicochemical properties on their size and structure, documented synthetic methodologies delivering NCs with atomic-level monodispersity and tailorable size and structural attributes at individual hierarchical levels are categorized and discussed. Such assured atomic-level modulation could confer metal NCs with novel application opportunities in diverse fields, which are also exemplified by their size- and structure-dictated catalytic and biomedical performance. The precise synthesis and application chemistry developed based on the hierarchical structure scheme of metal NCs could increase the acceptance of metal NCs as a new family of functional materials.

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Section: Catalytic and Biomedical Applications Of Metal Nanoclusterssupporting

confidence: 80%

Engineering Functional Metal Materials at the Atomic Level

et al. 2018

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“…Recently,N egishi et al synthesized as eries of Au n (GSH) NCs (n = 10, 15,18,22,25,29,33,39) and decorated them as co-catalyst onto BaLa 4 Ti 4 O 15 forw ater splitting. [211] They divided the obtained catalystsi nto two groups depending on the difference in number of Au atoms: group-1 (n = 10, 15,18,25,20) and group-2: (n = 22, 29, 33). Both groupsw ere annealeda t3 00 8C for 2h.A fter thermal treatment, the size distribution was determined using TEM.…”

Section: Mncs As Co-catalyst In Photocatalysisfor Water Splittingmentioning

confidence: 99%

Metal Nanoclusters: New Paradigm in Catalysis for Water Splitting, Solar and Chemical Energy Conversion

et al. 2019

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A sustainable future demands innovative breakthroughs in science and technology today, especially in the energy sector. Earth‐abundant resources can be explored and used to develop renewable and sustainable resources of energy to meet the ever‐increasing global energy demand. Efficient solar‐powered conversion systems exploiting inexpensive and robust catalytic materials for the photo‐ and photo‐electro‐catalytic water splitting, photovoltaic cells, fuel cells, and usage of waste products (such as CO2) as chemical fuels are appealing solutions. Many electrocatalysts and nanomaterials have been extensively studied in this regard. Low overpotentials, catalytic stability, and accessibility remain major challenges. Metal nanoclusters (NCs, ≤3 nm) with dimensions between molecule and nanoparticles (NPs) are innovative materials in catalysis. They behave like a “superatom” with exciting size‐ and facet‐dependent properties and dynamic intrinsic characteristics. Being an emerging field in recent scientific endeavors, metal NCs are believed to replace the natural photosystem II for the generation of green electrons in a viable way to facilitate the challenging catalytic processes in energy‐conversion schemes. This Review aims to discuss metal NCs in terms of their unique physicochemical properties, possible synthetic approaches by wet chemistry, and various applications (mostly recent advances in the electrochemical and photo‐electrochemical water splitting cycle and the oxygen reduction reaction in fuel cells). Moreover, the significant role that MNCs play in dye‐sensitized solar cells and nanoarrays as a light‐harvesting antenna, the electrochemical reduction of CO2 into fuels, and concluding remarks about the present and future perspectives of MNCs in the frontiers of surface science are also critically reviewed.

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“…39,40 Lately, Au, Ag and Pt NCs with different sizes also have been synthesized and used for photocatalytic applications. 41,42 However, there are very limited reports on the use of metals NCs immobilized on conducting surfaces for electro-and photocatalysis. 43 Herein we report the use of well characterized Ni NCs, Ni 4 (PET) 8 and Ni 6 (PET) 12 for anodic oxygen evolution reactions, demonstrating an example of efficient nanocrystals based electrocatalytic system for water oxidation.…”

Section: Introductionmentioning

confidence: 99%

Atomically monodisperse nickel nanoclusters as highly active electrocatalysts for water oxidation

et al. 2016

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Achieving water splitting at low overpotential with high oxygen evolution efficiency and stability is important for realizing solar to chemical energy conversion devices. Herein we report the synthesis, characterization and electrochemical evaluation of highly active nickel nanoclusters (Ni NCs) for water oxidation at low overpotential. These atomically precise and monodisperse Ni NCs are characterized by using UV-visible absorption spectroscopy, single crystal X-ray diffraction and mass spectrometry. The molecular formulae of these Ni NCs are found to be Ni4(PET)8 and Ni6(PET)12 and are highly active electrocatalysts for oxygen evolution without any pre-conditioning. Ni4(PET)8 are slightly better catalysts than Ni6(PET)12 and initiate the oxygen evolution at an amazingly low overpotential of ~1.51 V (vs RHE; η ≈ 280 mV). The peak oxygen evolution current density (J) of ~150 mA cm -2 at 2.0 V (vs. RHE) with a Tafel slope of 38 mV dec -1 is observed using Ni4(PET)8. These results are comparable to the state-of-the art RuO2 electrocatalyst, which is highly expensive and rare compared to Ni-based materials. Sustained oxygen generation for several hours with an applied current density of 20 mA cm -2 demonstrates the long-term stability and activity of these Ni NCs towards electrocatalytic water oxidation. This unique approach provides a facile method to prepare cost-effective, nanoscale and highly efficient electrocatalysts for water oxidation.

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Controlled Loading of Small Au_n Clusters (n = 10–39) onto BaLa₄Ti₄O₁₅ Photocatalysts: Toward an Understanding of Size Effect of Cocatalyst on Water-Splitting Photocatalytic Activity

Cited by 90 publications

References 53 publications

Engineering Functional Metal Materials at the Atomic Level

Engineering Functional Metal Materials at the Atomic Level

Metal Nanoclusters: New Paradigm in Catalysis for Water Splitting, Solar and Chemical Energy Conversion

Atomically monodisperse nickel nanoclusters as highly active electrocatalysts for water oxidation

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