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This study demonstrated that nickel-nanocluster catalysts exhibit 2.3 times higher electrocatalytic oxygen evolution reaction activity compared with nickel-oxide catalysts prepared using a general impregnation method on carbon black.

Membrane separation is making substantial contributions to water purification. Particularly important is the pore-size control designed for molecular sieving. Regarding water permeation, filtration experiments accentuate the importance of hydrophilic pores in enhancing the water adsorption capacity, while hydrophobic pores enable low-friction water diffusion. To reach both the criteria, we herein precisely design the pore metrics and pore functionalities to prepare a covalent organic framework (COF), termed TUS-46, membrane. Credited with pore sizes befitting for size-selective molecular exclusion and negative electrostatic pore walls, the TUS-46 COF membrane shows excellent rejection performance toward anionic dyes. Attributed to the free aldehyde functionalities in the framework resulting from unbalanced stoichiometry, the TUS-46 COF membrane also shows a 10-fold higher water permeance compared to the analogue COF membrane without free aldehyde functionalities. In particular, the in situ construction of hydrophilic nanospaces partaking in high water uptake and hydrophobic nanospaces facilitating fast water diffusion in a single COF structure endows the TUS-46 membranes with unprecedentedly high water flux. The stoichiometric imbalance approach presented herein offers a different route to COF membrane fabrication and may impart with an unprecedented control handle on the permeability and separation selectivity of COF membranes.

This study succeeded in obtaining three new thiolate protected metal nanoclusters by changing the ligand-exchange condition from previous studies.

AuRh alloy nanoparticles, prepared by simultaneous sputter deposition of Au and Rh metals on an ionic liquid, exhibited a surface composition-dependent electrocatalytic activity.

We have been aiming to reduce the amount of platinum (Pt) needed in catalysts for automobile exhaust-gas purification and fuel cell electrodes. To achieve this, we have attempted to: 1) establish s...

Suppressing the amount of carbon dioxide (CO2) in the atmosphere is an essential measure toward addressing global warming. Specifically, photocatalytic CO2 reduction reaction (CRR) is an effective strategy because it affords the conversion of CO2 into useful carbon feedstocks using sunlight and water. However, the practical application of photocatalyst-promoting CRR (CRR photocatalysts) requires significant improvement of their conversion efficiency. Accordingly, extensive research is being conducted toward the improvement of semiconductor photocatalysts, as well as cocatalysts that are loaded as active sites on the photocatalysts. In this review, we summarize recent research and development trends on the improvement of cocatalysts, which have a significant impact on the catalytic activity and selectivity of photocatalytic CRR. We expect that the advanced knowledge provided on the improvement of cocatalysts for CRR in this review will serve as a general guideline to accelerate the development of highly efficient CRR photocatalysts.

Metal nanoclusters composed of noble elements such as gold (Au) or silver (Ag) are regarded as superatoms. In recent years, the understanding of Au-based superatomic molecules has gradually progressed. However, there is still little information on Ag-based superatomic molecules. In the present study, we synthesise two di-superatomic molecules with Ag as the main constituent element and reveal the three essential conditions for the formation and isolation of a superatomic molecule comprising two Ag13−xMx structures (M = Ag or other metal; x = number of M) connected by vertex sharing. The effects of the central atom and the type of bridging halogen on the electronic structure of the resulting superatomic molecule are also clarified in detail. These findings are expected to provide clear design guidelines for the creation of superatomic molecules with various properties and functions.

Recently, the creation of new heterogeneous catalysts using the unique electronic/geometric structures of small metal nanoclusters (NCs) has received considerable attention. However, to achieve this, it is extremely important to establish methods to remove the ligands from ligand‐protected metal NCs while preventing the aggregation of metal NCs. In this study, the ligand‐desorption process during calcination was followed for metal‐oxide‐supported 2‐phenylethanethiolate‐protected gold (Au) 25‐atom metal NCs using five experimental techniques. The results clearly demonstrate that the ligand‐desorption process consists of ligand dissociation on the surface of the metal NCs, adsorption of the generated compounds on the support and desorption of the compounds from the support, and the temperatures at which these processes occurred were elucidated. Based on the obtained knowledge, we established a method to form a metal‐oxide layer on the surface of Au NCs while preventing their aggregation, thereby succeeding in creating a water‐splitting photocatalyst with high activity and stability., The ligand‐desorption process during calcination was elucidated for metal‐oxide‐supported thiolate‐protected gold (Au) 25‐atom metal nanoculusters (NCs) using five experimental techniques. Furthermore, based on obtained knowledge, a method was established to form a metal‐oxide layer on the surface of Au NCs while preventing their aggregation, thereby succeeding in creating a water‐splitting photocatalyst with high activity and stability.

Ligand-protected metal nanoclusters controlled by atomic accuracy (i. e. atomically precise metal NCs) have recently attracted considerable attention as active sites in heterogeneous catalysts. Using these atomically precise metal NCs, it becomes possible to create novel heterogeneous catalysts based on a size-specific electronic/geometrical structure of metal NCs and understand the mechanism of the catalytic reaction easily. However, to create high-performance heterogeneous catalysts using atomically precise metal NCs, it is often necessary to remove the ligands from the metal NCs. This review summarizes previous studies on the creation of heterogeneous catalysts using atomically precise metal NCs while focusing on the calcination as a ligand-elimination method. Through this summary, we intend to share state-of-art techniques and knowledge on (1) experimental conditions suitable for creating high-performance heterogeneous catalysts (e.g., support type, metal NC type, ligand type, and calcination temperature), (2) the mechanism of calcination, and (3) the mechanism of catalytic reaction over the created heterogeneous catalyst. We also discuss (4) issues that should be addressed in the future toward the creation of high-performance heterogeneous catalysts using atomically precise metal NCs. The knowledge and issues described in this review are expected to lead to clear design guidelines for the creation of novel heterogeneous catalysts.

With global warming and the depletion of fossil resources, our fossil-fuel-dependent society is expected to shift to one that instead uses hydrogen (H2) as clean and renewable energy. Water-splitting photocatalysts can produce H2 from water using sunlight, which are almost infinite on the earth. However, further improvements are indispensable to enable their practical application. To improve the efficiency of the photocatalytic water-splitting reaction, in addition to improving the semiconductor photocatalyst, it is extremely effective to improve the cocatalysts (loaded metal nanoclusters, NCs) that enable the reaction to proceed on the photocatalysts. We have thus attempted to strictly control metal NCs on photocatalysts by introducing the precise-control techniques of metal NCs established in the metal NC field into research on water-splitting photocatalysts. Specifically, the cocatalysts on the photocatalysts were controlled by adsorbing atomically precise metal NCs on the photocatalysts and then removing the protective ligands by calcination. This work has led to several findings on the electronic/geometrical structures of the loaded metal NCs, the correlation between the types of loaded metal NCs and the water-splitting activity, and the methods for producing high water-splitting activity. We expect that the obtained knowledge will lead to clear design guidelines for the creation of practical water-splitting photocatalysts and thereby contribute to the construction of a hydrogen-energy society.

Alloying has been studied actively for thiolate (SR)-protected metal nanoclusters (NCs) because heteroatom mixing enables the creation of novel electronic structures, physical/chemical properties, ...

The activity of many water‐splitting photocatalysts could be improved by the use of RhIII–CrIII mixed oxide (Rh2−xCrxO3) particles as cocatalysts. Although further improvement of water‐splitting activity could be achieved if the size of the Rh2−xCrxO3 particles was decreased further, it is difficult to load ultrafine (, Rh2−x Cr x O3 particles with a size of approximately 1.3 nm were loaded onto a BaLa4Ti4O15 photocatalyst. The photocatalyst exhibited the highest quantum yield reported for BaLa4Ti4O15. The developed preparation technique of Rh2−xCrxO3 particles is also expected to improve the activity of other advanced water‐splitting photocatalysts. SG=glutathionate.

Monolayer protected Au nanocluster catalysts are known to undergo structural changes during catalytic reactions, including dissociation and migration of ligands onto the support, which strongly affects their activity and stability. To better understand how the nature of ligands influences the catalytic activity of such catalysts, three types of ceria supported Au nanoclusters with different kinds of ligands (thiolates, phosphines and a mixture thereof) have been studied, employing CO oxidation as model reaction. The thiolate-protected Au

With global warming and the depletion of fossil resources, our fossil fuel-dependent society is expected to shift to one that instead uses hydrogen (H2) as a clean and renewable energy. To realize this, the photocatalytic water-splitting reaction, which produces H2 from water and solar energy through photocatalysis, has attracted much attention. However, for practical use, the functionality of water-splitting photocatalysts must be further improved to efficiently absorb visible (Vis) light, which accounts for the majority of sunlight. Considering the mechanism of water-splitting photocatalysis, researchers in the various fields must be employed in this type of study to achieve this. However, for researchers in fields other than catalytic chemistry, ceramic (semiconductor) materials chemistry, and electrochemistry to participate in this field, new reviews that summarize previous reports on water-splitting photocatalysis seem to be needed. Therefore, in this review, we summarize recent studies on the development and functionalization of Vis-light-driven water-splitting photocatalysts. Through this summary, we aim to share current technology and future challenges with readers in the various fields and help expedite the practical application of Vis-light-driven water-splitting photocatalysts.

The improvement of oxygen reduction reaction (ORR) catalysts is essential before polymer electrolyte fuel cells can be used widely. To this end, we established a simple method for the size-selective synthesis of a series of ligand-protected platinum nanoclusters with ∼1 nm particle size (Ptn NCs; n = ∼35, ∼51, and ∼66) and narrow size distribution (±∼4 Pt atoms) under atmospheric conditions. Using this method, each ligand-protected ∼1 nm Pt NC was obtained in a relatively high yield (nearly 80% for Pt∼66). We succeeded in adsorbing each ligand-protected ∼1 nm Pt NC on carbon black (CB) and then removing most of the ligands from the surface of the Pt NCs via calcination while maintaining the original size. The obtained Pt∼35/CB, Pt∼51/CB, and Pt∼66/CB exhibited ORR mass activities that were 1.6, 2.1, and 1.6 times higher, respectively, than that of commercial CB supported-Pt nanoparticles, and also display high durability.

In recent years, research on the use of metal nanoparticles (NPs) and nanoclusters (NCs) synthesized by liquid-phase reduction in water-splitting photocatalysts has been actively conducted. Water-splitting photocatalysts have been attracting attention because they can produce hydrogen (H2), which is attractive as a next-generation energy source, from solar energy and water. However, further improvement of water-splitting photocatalysts is required for their practical use in society. Recent studies have demonstrated that the active sites (cocatalysts) of water-splitting photocatalysts can be controlled using the advanced NP/NC syntheses and structural modulation techniques established in the fields of colloid, NP, and NC chemistry and thereby highly active water-splitting photocatalysts can be developed. If such research progresses further, it is expected that a transition to a new society using H2 as the main energy source will become possible. However, such applied research has just started and examples of such research are currently limited. The purpose of this review is to introduce the importance of controlled colloidal NPs/NCs in research on water-splitting photocatalysis to readers by summarizing the existing research. We hope that this review will raise interest in the application of metal NPs/NCs in water-splitting photocatalysis and that a society actively addressing energy and environmental problems will become a reality as soon as possible.

Although Pt is extensively used as a catalyst to purify automotive exhaust gas, it is desirable to reduce Pt consumption through size reduction because Pt is a rare element and an expensive noble metal. In this study, we successfully loaded a Pt17 cluster on γ-alumina (γ-Al2O3) (Pt17/γ-Al2O3) using [Pt17(CO)12(PPh3)8]Cln (n = 1, 2) as a precursor. In addition, we demonstrated that Pt is not present in the form of an oxide in Pt17/γ-Al2O3 but instead has a framework structure as a metal cluster. Moreover, we revealed that Pt17/γ-Al2O3 exhibits higher catalytic activity for carbon monoxide and propylene oxidation than γ-Al2O3-supported larger Pt nanoparticles (PtNP/γ-Al2O3) prepared using the conventional impregnation method. Recently, our group discovered a simple method for synthesizing the precursor [Pt17(CO)12(PPh3)8]Cln. Furthermore, Pt17 is a Pt cluster within the size range associated with high catalytic activity. By combining our established synthesis and loading methods, other groups can conduct further research on Pt17/γ-Al2O3 to explore its catalytic activities in greater depth.

If we wish to use metal clusters as magnetic materials and dipole materials, it is necessary to assemble the clusters to attain a certain material size. However, the types of building-block clusters suitable for assembly are currently very limited, and thereby we have little information on the factors required to assemble metal clusters and the physical properties and functions of such assembled structures. In this research, we found the following four points about thiolate (SR)-protected gold–platinum alloy (Au4Pt2) clusters ([Au4Pt2(SR)8]0); (1) [Au4Pt2(SR)8]0 is a metal cluster that can be used as a building block to form one-dimensional (1D) connected structures (1D-CS) via inter-cluster Au–Au bonds (aurophilic bond); (2) although all [Au4Pt2(SR)8]0 clusters have similar structures, the intra-cluster ligand interactions vary depending on the ligand structure. As a result, the distribution of the ligands in [Au4Pt2(SR)8]0 changes depending on the ligand structure; (3) the differences in the distributions of the ligands influence the inter-cluster ligand interactions, which in turn affects the formation of 1D-CS and changes the connected structure; and (4) the formation of 1D-CS decreases the band gap of the clusters. These results demonstrate that we need to design intra-cluster ligand interactions to produce 1D-CS with desired connecting structures.

Ionization of nanocrystals (NCs) causes both photoluminescence intermittency and a reduction in luminescence quantum efficiency and thus plays a critical role in the optoelectronic performance of NC-based devices. Here, we study the ionization and neutralization processes of CsPbBr3 perovskite NCs under strong photoexcitation by means of double-pump transient absorption spectroscopy. A strong initial pulse is used to generate ionized NCs, and their optical responses are investigated by varying the excitation intensity and delay time of the second pump pulse. We find that charging can occur either via nonradiative Auger recombination of biexcitons or via any possible recombination of trions. The presence of the extra charge inside of an ionized perovskite NC significantly reduces its absorption cross section. The experiments reveal that ionized NCs exhibit two types of neutralization processes with time constants on the order of nanoseconds and microseconds. These results are useful for the optimal design of NC-based photonic devices.

Icosahedral noble-metal 13-atom nanoclusters (NCs) can form connected structures, which can be regarded as superatomic molecules, by vertex sharing. However, there have been very few reports on the superatomic molecules formed using silver (Ag) as the base element. In this study, we synthesized [Ag

Metal nanoclusters (NCs), which consist of several, to about one hundred, metal atoms, have attracted much attention as functional nanomaterials for use in nanotechnology. Because of their fine particle size, metal NCs exhibit physical/chemical properties and functions different from those of the corresponding bulk metal. In recent years, many techniques to precisely synthesize metal NCs have been developed. However, to apply these metal NCs in devices and as next-generation materials, it is necessary to assemble metal NCs to a size that is easy to handle. Recently, multiple techniques have been developed to form one-, two-, and three-dimensional connected structures (CSs) of metal NCs through self-assembly. Further progress of these techniques will promote the development of nanomaterials that take advantage of the characteristics of metal NCs. This review summarizes previous research on the CSs of metal NCs. We hope that this review will allow readers to obtain a general understanding of the formation and functions of CSs and that the obtained knowledge will help to establish clear design guidelines for fabricating new CSs with desired functions in the future.

2-Phenylethanethiolate (PET) and 4-tert-butylbenzenethiolate (TBBT) are the most frequently used ligands in the study of thiolate (SR)-protected metal clusters. However, the effect of difference in the functional group between these ligands on the fundamental properties of the clusters has not been clarified. We synthesized [Au24Pt(TBBT)18]0, which has the same number of metal atoms, number of ligands, and framework structure as [Au24Pt(PET)18]0, by replacing ligands of [Au24Pt(PET)18]0 with TBBT. It was found that this ligand exchange is reversible unlike the case of other metal-core clusters. A comparison of the geometrical/electronic structure and stability of the clusters between [Au24Pt(PET)18]0 and [Au24Pt(TBBT)18]0 revealed three things with regard to the effect of ligand change from PET to TBBT on [Au24Pt(SR)18]0: (1) the induction of metal-core contraction and Au–S bond elongation, (2) no substantial effect on the HOMO–LUMO gap but a clear difference in optical absorption in the visible region, and (3) the decrease of stabilities against degradation in solution and under laser irradiation. By using these two clusters as model clusters, it is expected that the effects of the structural difference of ligand functional-groups on the physical properties and functions of clusters, such as catalytic ability and photoluminescence, would be clarified.

Infrared-light-induced carrier transfer is a key technology for ‘invisible’ optical devices for information communication systems and energy devices. However, clear and colourless photo-induced carrier transfer has not yet been demonstrated in the field of photochemistry, to the best of our knowledge. Here, we resolve this problem by employing short-wavelength-infrared (1400–4000 nm) localized surface plasmon resonance-induced electron injection from indium tin oxide nanocrystals to transparent metal oxides. The time-resolved infrared measurements visualize the dynamics of the carrier in this invisible system. Selective excitation of localized surface plasmon resonances causes hot electron injection with high efficiency (33%) and long-lived charge separation (~ 2–200 μs). We anticipate our study not only provides a breakthrough for plasmonic carrier transfer systems but may also stimulate the invention of state-of-the-art invisible optical devices., 赤外光を電気エネルギーや信号に変換する無色透明な材料の開発に成功 --見えない電子デバイスの開発へ道--. 京都大学プレスリリース. 2019-02-13., An Author Correction to this article was published on 17 April 2019. https://doi.org/10.1038/s41467-019-09888-2

Lead halide perovskite (APbX3) nanocrystals exhibit photoluminescence (PL) with both wide wavelength tunability and high quantum efficiency. While the Pb–X6 octahedra mainly determines the near-ban...

Metal nanoclusters (NCs) have a particle size of about one nanometer, which makes them the smallest unit that can give a function to a substance. In addition, metal NCs possess physical and chemical properties that are different from those of the corresponding bulk metals. Metal NCs with such characteristics are expected to be important for use in nanotechnology. Research on the precise synthesis of metal NCs and elucidation of their physical/chemical properties and functions is being actively conducted. When metal NCs are alloyed, it is possible to obtain further various electronic and geometrical structures and functions. Thus, research on alloy NCs has become a hot topic in the study of metal NCs and the number of publications on alloy NCs has increased explosively in recent years. Such publications have provided much insight into the effects of alloying on the electronic structure and function of metal NCs. However, the rapid increase in knowledge has made it difficult for researchers (especially those new to the field) to grasp all of it. Therefore, in this review, we summarize the reported chemical composition, geometrical structure, electronic structure, and physical and chemical properties of Aun-x Mx (SR)m , Agn-x Mx (SR)m , Aun-x Mx (PR3 )l (SR)m , and Agn-x Mx (PR3 )l (SR)m (Au=gold, Ag=silver, M=heteroatom, PR3 =phosphine, and SR=thiolate) NCs. This review is expected to help researchers understand the characteristics of alloy NCs and lead to clear design guidelines to develop new alloy NCs with intended functions.

Fine metal clusters have attracted much attention from the viewpoints of both basic and applied science for many years because of their unique physical/chemical properties and functions, which differ from those of bulk metals. Among these materials, thiolate (SR)-protected gold clusters (Aun(SR)m clusters) have been the most studied metal clusters since 2000 because of their ease of synthesis and handling. However, in the early 2000s, it was not easy to isolate these metal clusters. Therefore, high-resolution separation methods were explored, and several atomic-level separation methods, including polyacrylamide gel electrophoresis (PAGE), high-performance liquid chromatography (HPLC), and thin-layer chromatography (TLC), were successively established. These techniques have made it possible to isolate a series of Aun(SR)m clusters, and much knowledge has been obtained on the correlation between the chemical composition and fundamental properties such as the stability, electronic structure, and physical properties of Aun(SR)m clusters. In addition, these high-resolution separation techniques are now also frequently used to evaluate the distribution of the product and to track the reaction process. In this way, high-resolution separation techniques have played an essential role in the study of Aun(SR)m clusters. However, only a few reviews have focused on this work. This review focuses on PAGE, HPLC, and TLC separation techniques, which offer high resolution and repeatability, and summarizes previous studies on the high-resolution separation of Aun(SR)m and related clusters with the purpose of promoting a better understanding of the features and the utility of these techniques.

To establish an ultimate energy conversion system consisting of a water-splitting photocatalyst and a fuel cell, it is necessary to further increase the efficiencies of the hydrogen evolution reaction (HER), the oxygen evolution reaction (OER), and the oxygen reduction reaction (ORR). Recently, it was demonstrated that thiolate (SR)-protected gold clusters, Aun(SR)m, and their related alloy clusters can serve as model catalysts for these three reactions. However, as the previous data have been obtained under different experimental conditions, it is difficult to use them to gain a deep understanding of the means to attain higher activity in these reactions. Herein, we measured the HER, OER, and ORR activities of Aun(SR)m and alloy clusters containing different numbers of constituent atoms, ligand functional groups, and heteroatom species under identical experimental conditions. We obtained a comprehensive set of results that illustrates the effect of each parameter on the activities of the three reactions. Comparison of the series of results revealed that decreasing the number of constituent atoms in the cluster, decreasing the thickness of the ligand layer, and substituting Au with Pd improve the activities in all reactions. Taking the stability of the cluster into consideration, [Au24Pd(PET)18]0 (PET = 2-phenylethanethiolate) can be considered as a metal cluster with high potential as an HER, OER, and ORR catalyst. These findings are expected to provide clear design guidelines for the development of highly active HER, OER, and ORR catalysts using Aun(SR)m and related alloy clusters, which would allow realization of an ultimate energy conversion system.

Lead halide perovskite nanocrystals (NCs) are one of the most anticipated and promising materials for light-emitting diodes and lasers because of their high photoluminescence quantum yields (PLQYs). However, the formation of trions (charged excitons) in the NCs reduces their PLQYs. Here, we clarify the trion formation mechanism in perovskite CsPbBr3 NCs by analyzing the excitation fluence dependence of transient absorption signals. Under weak photoexcitation, trions are formed by charge carrier trapping at surface states. In contrast, biexciton Auger recombination dominates the trion formation under strong photoexcitation. We found that the postsynthetic surface treatment suppresses the extrinsic surface-related formation of trions. The thorough understanding of the trion formation mechanisms is essential for the PLQY improvement of perovskite NCs and helps to reduce ionization of NCs in solid-state devices.

Combining the superior optical properties of their bulk counterparts with quantum confinement effects, lead halide perovskite nanocrystals are unique laser materials with low-threshold optical gain. In such nonlinear optical regimes, multiple excitons are generated in the nanocrystals and strongly affect the optical gain through many-body interactions. Here, we investigate the exciton–exciton interactions in CsPbI3 nanocrystals by femtosecond transient absorption spectroscopy. From the analysis of the induced absorption signal observed immediately after the pump excitation, we estimated the binding energy for the hot biexcitons that are composed of an exciton at the band edge and a hot exciton generated by the pump pulse. We found that the exciton–exciton interaction becomes stronger for hot excitons with greater excess energies and that the optical gain can be controlled by changing the excess energy of the hot excitons.