Single-Atom Titanium on Mesoporous Nitrogen, Oxygen-Doped Carbon for Efficient Photo-thermal Catalytic CO2 Cycloaddition by a Radical Mechanism.

Developing efficient and earth-abundant catalysts for CO2 fixation to high value-added chemicals is meaningful but challenging. Styrene carbonate has great market value, but the cycloaddition of CO2 to styrene oxide is difficult due to the high steric hindrance and weak electron-withdrawing ability of the phenyl group. To utilize clean energy (such as optical energy) directly and effectively for CO2 value-added process, we introduce earth-abundant Ti single-atom into the mesoporous nitrogen, oxygen-doped carbon nanosheets (Ti-CNO) by a two-step method. The Ti-CNO exhibits excellent photothermal catalytic activities and stability for cycloaddition of CO2 and styrene oxide to styrene carbonate. Under light irradiation and ambient pressure, an optimal Ti-CNO produces styrene carbonate with a yield of 98.3 %, much higher than CN (27.1 %). In addition, it shows remarkable stability during 10 consecutive cycles. Its enhanced catalytic performance stems from the enhanced photothermal effect and improved Lewis acidic/basic sites exposed by the abundant mesopores. The experiments and theoretical simulations demonstrate the styrene oxide⋅+ and CO2⋅- radicals generated at the Lewis acidic (Tiδ+) and basic sites of Ti-CNO under light irradiation, respectively. This work furnishes a strategy for synthesizing advanced single-atom catalysts for photo-thermal synergistic CO2 fixation to high value products via a cycloaddition pathway.

Cu-based catalysts with the co-existence of single atoms and nanoparticles for basic electrocatalytic oxygen reduction reaction.

Developing efficient and stable oxygen reduction reaction (ORR) catalysts to replace the precious Pt/C is very important for the industrial application of proton-exchange membrane fuel cells. Herein, using bismuth-based metal-organic frameworks as the substrate to disperse copper ions, we prepared a catalyst containing both Cu single atoms and Cu nanoparticles (CuSACuNP/BiCN) by a pyrolysis method. In 0.1 M KOH electrolyte, the electrocatalytic ORR performance of CuSACuNP/BiCN was superior to that of commercial Pt/C. With a hierarchical porous architecture, CuSACuNP/BiCN displayed a half-wave potential of 0.86 V vs. RHE and a diffusion-limiting current density of 5.82 mA cm-2 with a four-electron transfer process. In addition, it was stable during a 12-hour durability test. This study provides guidance for the synthesis of advanced Cu-based nano-single-atom catalytic materials for ORR applications.

Single-Atom Gadolinium Nano-Contrast Agents with High Stability for Tumor T1 Magnetic Resonance Imaging.

Gadolinium chelates for tumor magnetic resonance imaging (MRI) face challenges such as inadequate sensitivity, lack of selectivity, and risk of Gd leakage. This study presents a single-atom Gd nano-contrast agent (Gd-SA) that enhances tumor MRI. Isolated Gd atoms coordinated by six N atoms and two O atoms are atomically dispersed on a hollow carbon nanosphere, allowing the maximum utilization of Gd atoms with reduced risk of toxic Gd ion leakage. Owning to the large surface area and fast exchange of relaxed water molecules, Gd-SA shows excellent T1-weighted magnetic resonance enhancement with a r1 value of 11.05 mM-1 s-1 at 7 T, which is 3.6 times that of the commercial gadolinium-diethylenetriamine pentaacetic acid (Gd-DTPA). In vivo MRI results show that the Gd-SA has a higher spatial resolution and a wider imaging time window for tumors than Gd-DTPA, with low hematological, hepatic, and nephric toxicities. These advantages demonstrate the great potential of single-atom Gd-based nanomaterials as safe, efficient, and long-term MRI contrast agents for cancer diagnosis.

Pt Atomic Layers with Tensile Strain and Rich Defects Boost Ethanol Electrooxidation.

Surface and strain engineering are two effective strategies to improve performance; however, synergetic controls of surface and strain effects remains a grand challenge. Herein, we report a highly efficient and stable electrocatalyst with defect-rich Pt atomic layers coating an ordered Pt3Sn intermetallic core. Pt atomic layers enable the generation of 4.4% tensile strain along the [001] direction. Benefiting from synergetic controls of surface and strain engineering, Pt atomic-layer catalyst (Ptatomic-layer) achieves a remarkable enhancement on ethanol electrooxidation performance with excellent specific activity of 5.83 mA cm-2 and mass activity of 1166.6 mA mg Pt-1, which is 10.6 and 3.6 times higher than the commercial Pt/C, respectively. Moreover, the intermetallic core endows Ptatomic-layer with outstanding durability. In situ infrared reflection-absorption spectroscopy as well as density functional theory calculations reveal that tensile strain and rich defects of Ptatomci-layer facilitate to break C-C bond for complete ethanol oxidation for enhanced performance.

Synergetic Dual-Atom Catalysts: The Next Boom of Atomic Catalysts.

Dual-atom catalysts (DACs) are an important branch of single-atom catalysts (SACs), in which the former can effectively break the dilemma faced by the traditional SACs. The synergetic effects between bimetallic atoms provide many active sites, promising to improve catalytic performance and even catalyze more complex reactions. This paper reviews the recent research progresses of two kinds of DACs, including homonuclear and heteronuclear DACs, and their applications in oxygen reduction, carbon dioxide reduction, hydrogen evolution, oxygen evolution, Zn-air batteries, tandem catalytic reactions, and so on. In addition, in order to promote the further development of DACs, the challenges and perspectives of DACs are put forward.

Cation Exchange Enabled Cu Dopants Location Tailoring and Photoelectric Properties Regulation in CdS Nanosheets.

Doping-related point defect engineering in low-dimensional semiconductor nanostructures is important to regulate their optical and electronic properties. The substitutional or interstitial location of heterovalent dopants is critical and has not been controlled effectively yet. Herein, we carefully control the kinetics of reverse cation exchange between CuxS 2D nanosheets and ligand-coordinated Cd2+ cations to control the Cu doping sites in CdS nanosheets (NSs). The substitutional and interstitial Cu dopants were directly confirmed by spherical aberration-corrected TEM (SACTEM) and their X-ray absorption spectroscopy (XAS) coordination investigation. Density functional theory (DFT) calculations and their experimental conductivities and dopant luminescence performance demonstrated the dramatic differences that are due to the location of different Cu dopants. These findings provide deeper insights on dopants' location regulation in a nanostructured host semiconductor.

Atomically dispersed Ru in Pt3Sn intermetallic alloy as an efficient methanol oxidation electrocatalyst.

We successfully fabricate a novel concave nanostructure that is composed of atomically dispersed Ru atoms in Pt3Sn nanoconcaves (Ru-Pt3Sn NCs), which shows enhanced performance in methanol electroxidation compared to commercial Pt/C. This could be ascribed to the stable intermetallic structure and active surface structure, as well as the synergy among Pt, Sn and Ru.

Catalytic Nanomaterials toward Atomic Levels for Biomedical Applications: From Metal Clusters to Single-Atom Catalysts.

Single-atom catalysts (SACs) featuring the complete atomic utilization of metal, high-efficient catalytic activity, superior selectivity, and excellent stability have been emerged as a frontier in the catalytic field. Recently, increasing interests have been drawn to apply SACs in biomedical fields for enzyme-mimic catalysis and disease therapy. To fulfill the demand of precision and personalized medicine, precisely engineering the structure and active site toward atomic levels is a trend for nanomedicines, promoting the evolution of metal-based biomedical nanomaterials, particularly biocatalytic nanomaterials, from nanoparticles to clusters and now to SACs. This review outlines the syntheses, characterizations, and catalytic mechanisms of metal clusters and SACs, with a focus on their biomedical applications including biosensing, antibacterial therapy, and cancer therapy, as well as an emphasis on their in vivo biological safeties. Challenges and future perspectives are ultimately prospected for SACs in diverse biomedical applications.

Synthetic strategies of supported atomic clusters for heterogeneous catalysis.

Supported atomic clusters with uniform metal sites and definite low-nuclearity are intermediate states between single-atom catalysts (SACs) and nanoparticles in size. Benefiting from the presence of metal-metal bonds, supported atomic clusters can trigger synergistic effects among every metal atom, which contributes to achieving unique catalytic properties different from SACs and nanoparticles. However, the scalable and precise synthesis and atomic-level insights into the structure-properties relationship of supported atomic clusters is a great challenge. This perspective presents the latest progress of the synthesis of supported atomic clusters, highlights how the structure affects catalytic properties, and discusses the limitations as well as prospects.

Highly Selective Photoreduction of CO2 with Suppressing H2 Evolution by Plasmonic Au/CdSe-Cu2 O Hierarchical Nanostructures under Visible Light.

Here, the photocatalytic CO2 reduction reaction (CO2 RR) with the selectivity of carbon products up to 100% is realized by completely suppressing the H2 evolution reaction under visible light (λ > 420 nm) irradiation. To target this, plasmonic Au/CdSe dumbbell nanorods enhance light harvesting and produce a plasmon-enhanced charge-rich environment; peripheral Cu2 O provides rich active sites for CO2 reduction and suppresses the hydrogen generation to improve the selectivity of carbon products. The middle CdSe serves as a bridge to transfer the photocharges. Based on synthesizing these Au/CdSe-Cu2 O hierarchical nanostructures (HNSs), efficient photoinduced electron/hole (e- /h+ ) separation and 100% of CO selectivity can be realized. Also, the 2e- /2H+ products of CO can be further enhanced and hydrogenated to effectively complete 8e- /8H+ reduction of CO2 to methane (CH4 ), where a sufficient CO concentration and the proton provided by H2 O reduction are indispensable. Under the optimum condition, the Au/CdSe-Cu2 O HNSs display high photocatalytic activity and stability, where the stable gas generation rates are 254 and 123 µmol g-1 h-1 for CO and CH4 over a 60 h period.

Facet engineering in metal organic frameworks to improve their electrochemical activity for water oxidation.

The facet effect has been well demonstrated for nanocrystal catalysis, however it is rarely revealed in metal organic frameworks (MOFs). Herein, we present a facile way to construct 2D zeolitic imidazolate framework-67 (ZIF-67) with dominant exposure of the (002) facets. We discovered that the ZIF-67 (002) facet exhibited the highest catalytic activity for oxygen evolution reaction (OER) among the (002), (011), and (111) facets. Moreover, this facet engineering is also available for ZIF-8 nanocrystals.

Ultrafine PtRu Dilute Alloy Nanodendrites for Enhanced Electrocatalytic Methanol Oxidation.

Dilute alloy nanostructures have been demonstrated to possess distinct catalytic properties. Noble-metal-induced reduction is one effective synthesis strategy to construct dilute alloys and modify the catalytic performance of the host metal. Herein, we report the synthesis of ultrafine PtRu dilute alloy nanodendrites (PtRu NDs, molar ratio Ru/Pt is 1:199) by the reduction of RuIII ions induced by Pt metal. For the methanol oxidation reaction, PtRu NDs showed the highest forward peak current density (2.66 mA cm-2 , 1.14 A/mgPt ) and the best stability compared to those of pure-Pt nanodendrites (pure-Pt NDs), commercial PtRu/C and commercial Pt/C catalysts.

Bismuth Single Atoms Resulting from Transformation of Metal-Organic Frameworks and Their Use as Electrocatalysts for CO2 Reduction.

The electrocatalytic reduction reaction of CO2 (CO2RR) is a promising strategy to promote the global carbon balance and combat global climate change. Herein, exclusive Bi-N4 sites on porous carbon networks can be achieved through thermal decomposition of a bismuth-based metal-organic framework (Bi-MOF) and dicyandiamide (DCD) for CO2RR. Interestingly, in situ environmental transmission electron microscopy (ETEM) analysis not only directly shows the reduction from Bi-MOF into Bi nanoparticles (NPs) but also exhibits subsequent atomization of Bi NPs assisted by the NH3 released from the decomposition of DCD. Our catalyst exhibits high intrinsic CO2 reduction activity for CO conversion, with a high Faradaic efficiency (FECO up to 97%) and high turnover frequency of 5535 h-1 at a low overpotential of 0.39 V versus reversible hydrogen electrode. Further experiments and density functional theory results demonstrate that the single-atom Bi-N4 site is the dominating active center simultaneously for CO2 activation and the rapid formation of key intermediate COOH* with a low free energy barrier.

Enhancement of the complex third-order nonlinear optical susceptibility in Au nanorods.

We experimentally determined the dispersion of the complex third-order nonlinear optical susceptibility χ(3) of Au nanorods over a wide bandwidth (370 - 800 nm). Compared to bulk Au, these nanorods exhibit greatly enhanced nonlinearities that can be manipulated by geometrical parameters. Accurately measuring the χ(3) values of nanostructured metals is challenging because χ(3) is strongly influenced by the local field effects. Hence the current published χ(3) values for Au nanorods have huge variations in both magnitude and sign because Z-scan measurements are used almost exclusively. This work combines pump-probe methods with spectroscopic ellipsometry to show that Au nanorods exhibit strong wavelength dependence and enhanced χ(3) in the vicinity of the longitudinal plasmon mode and explains where the regions of SA and RSA exist and how focusing and defocusing affects χ(3). In this context, the results highlight the importance of the dispersion of the quantity χ(3) to design plasmonic platforms for nanophotonics applications.

Evolution of Hollow CuInS2 Nanododecahedrons via Kirkendall Effect Driven by Cation Exchange for Efficient Solar Water Splitting.

Hollow-structured semiconductor nanocrystals (NCs) have aroused tremendous research interest because of their compelling structure-related properties that can facilitate the development of many important applications including solar water splitting. However, the creation of multicomponent semiconductor NCs (such as I-III-VI2 and I2-II-IV-VI4 semiconductors) possessing a hollow architecture still remains a great challenge because of the difficulty in balancing the reactivities of multiple precursors. In this study, we report an effective strategy to prepare hollow CuInS2 nanododecahedrons featuring high uniformity in morphology and composition, based on the Kirkendall effect driven by the cation exchange between Cu+ and In3+ using Cu2-xS nanododecahedrons as templates. The unequal diffusion rates of cations result in an inward flux of vacancies favorably along the (0 16 0) facets of Cu2-xS dodecahedrons, forming a Cu2-xS@CuInS2 core-shell intermediate with striped voids in the core region. Optical absorption studies and photoelectrochemical measurements imply that the increase in the hollowing degree of the NCs benefits enhanced light harvesting and separation of photogenerated charge carriers. As a result, the obtained hollow CuInS2 nanododecahedrons present a high activity in photocatalytic hydrogen evolution, much superior to previously reported CuInS2 photocatalysts with different architectures. We envision that the multifarious morphologies attainable for the Cu2-xS NC templates and the advantages of Cu+ for cation exchange can make this method adaptable to a vast variety of previously intractable structures and compositions.

High-Performance Quantum Dots with Synergistic Doping and Oxide Shell Protection Synthesized by Cation Exchange Conversion of Ternary-Composition Nanoparticles.

The insertion of cation impurities into quantum dots (QDs) as a dopant has been proved to be an efficient way to tailor their optical, electronic, and magnetic properties; however, the low quantum yield (QY) and poor photostability strongly limit their further applications. We report a strategy to coat a thin oxide shell around the heterovalent doped QDs to enhance their QYs and photostabilities simultaneously. In the case of Ag+-doped CdS QDs, the controlled cation exchange reaction between Cd2+ and ternary Ag3SbS3 nanoparticles not only realizes the Ag+ doping in CdS QDs but also generates a thin Sb2O3 shell around the surface of the QDs. Enabled by such, as-prepared CdS:Ag@Sb2O3 QDs exhibited enhanced photostability and high QY of 66.5%. We envision that the findings presented here will inspire more novel protocols for advancing the practical applications of doped QDs.

Semiconductor Nanocrystal Engineering by Applying Thiol- and Solvent-Coordinated Cation Exchange Kinetics.

Thiol- and solvent-coordinated cation exchange kinetics have been applied to engineer the composition and crystallinity of novel nanocrystals. The detailed thermodynamics and kinetics of the reactions were explored by NMR spectroscopy, time-dependent photoluminescence (PL) characterizations and theoretical simulations. The fine structure of the colloidal semiconductor nanocrystals (CSNCs) was investigated by X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). In this way, high-quality p-type Ag-doped ZnS quantum dots (QDs) and Au@ZnS hetero-nanocrystals with a cubic phase ZnS shell were synthesized successfully.The unprecedented dominant Ag+ -dopant-induced fluorescence and p-type conductivity in the zinc-blende ZnS are reported.

Porous platinum-silver bimetallic alloys: surface composition and strain tunability toward enhanced electrocatalysis.

Promoting surface strains in heterogeneous catalysts and heteroatomic interactions in alloying offer an effective strategy for the development of electrocatalysts with greatly enhanced activity. In this work, we design platinum-silver nanotubes (PtAg NTs) with tunable surface compositions by a controlled galvanic replacement reaction of well-defined Ag nanowires (NWs). The optimized and porous PtAg NTs (PtAg-4 NTs), with the Pt5Ag3 surface composition and (111) facet-dominant surface features, exhibit an extraordinary oxygen reduction reaction (ORR) activity that reaches a specific activity of 1.13 mA cm-2 and a mass activity of 0.688 A mg-1Pt at 0.9 V versus a reversible hydrogen electrode (RHE), which are 4.5 times and 4.3 times those of commercial Pt/C catalysts (0.25 mA cm-2 and 0.16 A mg-1Pt). Moreover, PtAg-4 NTs/C can endure under the ORR conditions over the course of 10 000 cycles with negligible activity decay. Remarkably, density functional theory simulations reveal that the porous PtAg-4 NTs exhibit enhanced adsorption interaction with adsorbates, attributed to the catalytically active sites on high-density (111) facets and modulation of the surface strain, further boosting the ORR activity and durability.

Near-Infrared Luminescent Ternary Ag3 SbS3 Quantum Dots by in situ Conversion of Ag Nanocrystals with Sb(C9 H19 COOS)3.

Differently from the normal three single precursor method to produce colloidal ternary quantum dots (QDs), herein ternary Ag3 SbS3 quantum dots (QDs) with efficient near-infrared (NIR) luminescence have been prepared by a new facile in situ conversion of Ag nanocrystals (NCs) with a binary Sb/S organic precursor Sb(C9 H19 COOS)3 under low temperature. The unprecedented construction evolution from Ag NCs to Ag3 SbS3 /Ag hetero-structure and final monodisperse Ag3 SbS3 QDs has been demonstrated. These novel Ag3 SbS3 QDs exhibit efficient NIR emission at ≈1263 nm and possess high colloidal stability.

Phosphine ligand-mediated kinetics manipulation of aqueous cation exchange: a case study on the synthesis of Au@SnSx core-shell nanocrystals for photoelectrochemical water splitting.

Au@Sn2S3 and Au@SnS2 core-shell hybrid nanocrystals (HNCs) were respectively accessed via an aqueous cation exchange-mediated growth strategy by using different phosphine ligands. The choice of proper ligands during synthesis is imperative to optimize the photoelectrochemical performance of these previously hardly accessible HNCs that manifest compelling plasmon-exciton interactions.