Atomically precise Au25(GSH)18 nanoclusters versus plasmonic Au nanocrystals: Evaluating charge impetus in solar water oxidation

Atomically precise metal nanoclusters (NCs) have been deemed as an emerging class of metal nanomaterials owing to fascinating size-dependent physicochemical properties, discrete energy band structure, and quantum confinement effect, which are distinct from conventional metal nanoparticles (NPs). Nevertheless, metal NCs suffer from photoinduced self-oxidative aggregation accompanied by in-situ transformation to metal NPs, markedly reducing the photosensitization of metal NCs. Herein, maneuvering the generic instability of metal NCs, we perform the charge transport impetus comparison between atomically precise metal NCs and plasmonic metal NPs counterpart obtained from in-situ self-transformation of metal NCs in photoelectrochemical (PEC) water splitting reaction. For conceptual demonstration, we proposed two quintessential heterostructures, which include TNTAs-Au₂₅ heterostructure fabricated by electrostatically depositing glutathione (GSH)-protected Au₂₅(GSH)₁₈ NCs on the TiO₂ nanotube arrays (TNTAs) substrate, and TNTAs-Au heterostructure constructed by triggering self-transformation of Au₂₅(GSH)₁₈ NCs to plasmonic Au NPs in TNTAs-Au₂₅ via calcination. The results indicate that photoelectrons produced over Au₂₅ NCs are superior to hot electrons of plasmonic Au NPs in stimulating the interracial charge transport toward solar water oxidation. This is mainly ascribed to the significantly accelerated carrier transport kinetics, prolonged carrier lifespan, and substantial photosensitization effect of Au₂₅ NCs compared with plasmonic Au NPs, resulting in the considerably enhanced PEC water splitting performance of TNTAs-Au₂₅ relative to plasmonic TNTAs-Au counterpart under visible light irradiation. Our work would provide important implications for rationally designing atomically precise metal NCs-based photosystems toward solar energy conversion.     

Carbon Monoxide: A Mild and Efficient Reducing Agent towards Atomically Precise Gold Nanoclusters

In recent years, thiolate‐protected gold nanoclusters (or thiolated Au NCs) with a core size below 2 nm have emerged as a new class of multifunctional nanoparticles because of their unique molecular‐like properties and the potential to use these properties in many practical applications. A general synthesis of Au NCs may involve the use of a strong reducing agent (e.g., sodium borohydride (NaBH₄)), which often leads to the formation of mix‐sized Au NCs if no delicate control is applied. To obtain atomically precise Au NCs, additional physical or chemical selection processes (e.g., high‐resolution separation or size‐focusing) are required, which are difficult to be scaled up or are limited to only thermodynamically stable products. By introducing a milder reducing agent – carbon monoxide (CO) – both stable and metastable thiolated Au NCs, including Au_10–12, Au₁₅, Au₁₈, Au₂₅, and Au₂₉, can be synthesized in a one‐pot manner. In addition, CO reduction also enables the synthesis of a highly luminescent Au₂₂(SG)₁₈ NC. Furthermore, the intermediates of Au NC growth can be tracked in the CO‐reduction system due to the mild and readily stoppable nature of CO reduction. Therefore, the use of CO reduction may bring new flexibilities in designing synthetic strategies and understanding the growth mechanism of atomically precise Au NCs, which could contribute to a better design of functional Au NCs, further paving their way towards practical applications in various fields.     

Constructing a coplanar heterojunction through enhanced π-π conjugation in g-C3N4 for efficient solar-driven water splitting

Adjusting the electronic structure of graphitic carbon nitride（g-C₃N₄） photocatalyst through π-π conjugation is an effective method to achieve efficient photogenerated carrier separation. One key challenge ofπ-π conjugation control is to tune the degree of such conjugation without destroying the g-C₃N₄structure. Herein we report a conceptual design that achieves a coplanar heterojunction by enhancing theπ-π conjugation via the doping of crystalline g-C...     

Aurophilic Interactions in the Self‐Assembly of Gold Nanoclusters into Nanoribbons with Enhanced Luminescence

Aurophilic interactions (Au^I???Au^I) are crucial in directing the supramolecular self‐assembly of many gold(I) compounds; however, this intriguing chemistry has been rarely explored for the self‐assembly of nanoscale building blocks. Herein, we report on studies on aurophilic interactions in the structure‐directed self‐assembly of ultrasmall gold nanoparticles or nanoclusters (NCs, <2 nm) using [Au₂₅(SR)₁₈]^? (SR=thiolate ligand) as a model cluster. The self‐assembly of NCs is initiated by surface‐motif reconstruction of [Au₂₅(SR)₁₈]^? from short SR‐[Au^I‐SR]₂ units to long SR‐[Au^I‐SR]_x (x>2) staples accompanied by structure modification of the intrinsic Au₁₃ kernel. Such motif reconstruction increases the content of Au^I species in the protecting shell of Au NCs, providing the structural basis for directed aurophilic interactions, which promote the self‐assembly of Au NCs into well‐defined nanoribbons in solution. More interestingly, the compact structure and effective aurophilic interactions in the nanoribbons significantly enhance the luminescence intensity of Au NCs with an absolute quantum yield of 6.2 % at room temperature.     

Hydrochromic CsPbBr3 Nanocrystals for Anti‐Counterfeiting

Hydrochromic materials that can reversibly change color upon water treatment have attracted much attention owing to their potential applications in diverse fields. Herein, for the first time, we report that space‐confined CsPbBr₃ nanocrystals (NCs) are hydrochromic. When CsPbBr₃ NCs are loaded into a porous matrix, reversible transition between luminescent CsPbBr₃ and non‐luminescent CsPb₂Br₅ can be achieved upon the exposure/removal of water. The potential applications of hydrochromic CsPbBr₃ NCs in anti‐counterfeiting are demonstrated by using CsPbBr₃ NCs@mesoporous silica nanospheres (around 100 nm) as the starting material. Owing to the small particle size and negatively charged surface, the as‐prepared particles can be laser‐jet printed with high precision and high speed. We demonstrate the excellent stability over repeated transformation cycles without color fade. This new discovery may not only deepen the understanding of CsPbX₃, but also open a new way to design CsPbX₃ materials for new applications.     

Photothermal Oxidation of Cinnamyl Alcohol with Hydrogen Peroxide Catalyzed by Gold Nanoparticle/Antimony-Doped Tin Oxide Nanocrystals

Gold nanoparticles with different mean sizes were formed on antimony-doped tin oxide nanocrystals by the temperature-varied deposition-precipitation method (Au/ATO NCs). Au/ATO NCs possess strong absorption in the near-infrared region due to Drude excitation in addition to the localized surface plasmon resonance (LSPR) of AuNPs around 530 nm. Au/ATO NCs show thermally activated catalytic activity for the oxidation of cinnamyl alcohol to cinnamaldehyde by hydrogen peroxide. The catalytic activity increases with a decrease in the mean Au particle size (d_Au) at 5.3 nm≤d_Au≤8.2 nm. Light irradiation (λ_ex >660 nm, ∼0.5 sun) of Au/ATO NCs increases the rate of reaction by more than twice with ∼95 % selectivity. Kinetic analyses indicated that the striking enhancement of the reaction stems from the rise in the temperature near the catalyst surface of ∼30 K due to the photothermal effect of the ATO NCs.     

Unraveling the Impact of Gold(I)–Thiolate Motifs on the Aggregation-Induced Emission of Gold Nanoclusters

Aggregation-induced emission (AIE) provides an efficient strategy to synthesize highly luminescent metal nanoclusters (NCs), however, rational control of emission energy and intensity of metal NCs is still challenging. This communication reveals the impact of surface Au^I-thiolate motifs on the AIE properties of Au NCs, by employing a series of water-soluble glutathione (GSH)-coordinated Au complexes and NCs as a model ([Au₁₀SR₁₀], [Au₁₅SR₁₃], [Au₁₈SR₁₄], and [Au₂₅SR₁₈]⁻, SR=thiolate ligand). Spectroscopic investigations show that the emission wavelength of Au NCs is adjustable from visible to the near-infrared II (NIR-II) region by controlling the length of the Au^I-SR motifs on the NC surface. Decreasing the length of Au^I-SR motifs also changes the origin of cluster luminescence from AIE-type phosphorescence to Au⁰-core-dictated fluorescence. This effect becomes more prominent when the degree of aggregation of Au NCs increases in solution.     

Unraveling the Impact of Gold(I)–Thiolate Motifs on the Aggregation‐Induced Emission of Gold Nanoclusters

Aggregation‐induced emission (AIE) provides an efficient strategy to synthesize highly luminescent metal nanoclusters (NCs), however, rational control of emission energy and intensity of metal NCs is still challenging. This communication reveals the impact of surface Au^I‐thiolate motifs on the AIE properties of Au NCs, by employing a series of water‐soluble glutathione (GSH)‐coordinated Au complexes and NCs as a model ([Au₁₀SR₁₀], [Au₁₅SR₁₃], [Au₁₈SR₁₄], and [Au₂₅SR₁₈]^?, SR=thiolate ligand). Spectroscopic investigations show that the emission wavelength of Au NCs is adjustable from visible to the near‐infrared II (NIR‐II) region by controlling the length of the Au^I‐SR motifs on the NC surface. Decreasing the length of Au^I‐SR motifs also changes the origin of cluster luminescence from AIE‐type phosphorescence to Au⁰‐core‐dictated fluorescence. This effect becomes more prominent when the degree of aggregation of Au NCs increases in solution.     

Solvent effect on the synthesis of monodisperse amine-capped Au nanoparticles

A remarkable solvent effect in a single-phase synthesis of monodisperse amine-capped Au nanoparticles is demonstrated.Oleylamine-capped Au nanoparticles were prepared via the reduction of HAuCU by an amine-borane complex in the presence of oleylamine in an organic solvent.When linear or planar hydrocarbon(e.g.,n-hexane,n-octane,1-octadecylene,benzene,and toluene) was used as the solvent, high-quality monodisperse Au nanoparticles with tunable sizes were obtained.However,Au nanoparticles with poor size dispersity were obtained when tetralin,chloroform or cyclohexane was used as the solvent.The revealed solvent effect allows the controlled synthesis of monodisperse Au nanoparticles with tunable size of 3-10 nm.     

Luminescent Noble Metal Nanoclusters as an Emerging Optical Probe for Sensor Development

In the past few years, highly luminescent noble metal nanoclusters (e.g., Au and Ag NCs or Au/Ag NCs in short) have emerged as a class of promising optical probes for the construction of high‐performance optical sensors because of their ultrasmall size (<2 nm), strong luminescence, good photostability, excellent biocompatibility, and unique metal‐core@ligand‐shell structure. In this Focus Review, we briefly summarize the common syntheses for water‐soluble highly‐luminescent thiolate‐ and protein‐protected Au/Ag NCs and their interesting luminescence properties, highlight recent progress in their use as optical sensors with an emphasis on the mechanisms underlying their selectivity, and finally discuss approaches to improving their sensitivity. The scope of the works surveyed is confined to highly luminescent thiolate‐ and protein‐protected Au/Ag NCs.     

Hydrogen Peroxide Assisted Synthesis of Highly Luminescent Sulfur Quantum Dots

An H₂O₂‐assisted top‐down approach is used to synthesize brightly luminescent, color‐tunable sulfur quantum dots (SQDs), with a photoluminescence quantum yield of up to 23 %. The formation of SQDs involves dissolution of bulk sulfur powder into small particles in an alkaline environment in the presence of polyethylene glycol, followed by H₂O₂‐assisted etching of polysulfide species, which has the advantage of the passivation of surface states. This synthetic strategy allows us to simultaneously control the final size of SQDs, to tune their emission color, and to improve their emission quantum yield by eliminating surface traps. Down‐conversion white light emitting diodes were also fabricated using blue emissive SQDs and orange emissive copper nanoclusters, with CIE color coordinates of (0.33, 0.32) and a high color rendering index of 91. The water‐soluble, highly luminescent SQDs are promising luminescent materials that can be produced from abundant precursor materials.     

Efficient and Stable Thin-Film Luminescent Solar Concentrators Enabled by Near-Infrared Emission Perovskite Nanocrystals

A novel triphenylphosphine (TPP) treatment strategy was developed to prepare the near-infrared emission CsPbI₃ nanocrystal (NC)-polymer composite thin-film luminescent solar concentrators (LSCs) featuring high absolute photoluminescence quantum yield (PLQY), low reabsorption, and high stability. The PL emission of the LSCs is centered at about 700 nm with 99.4±0.4 % PLQY and narrow full width at half maximum (FWHM) of 75 meV (30 nm). Compared with LSCs prepared with classic CsPbI₃ NCs, the stability of the LSCs after TPP treatments has been greatly improved, even after long-term (30 days) immersion in water and strong mercury-lamp irradiation (50 mW cm⁻²). Owing to the presence of lone-pair electrons on the phosphorus atom, TPP is also used as a photoinitiator, with higher efficiency than other common photoinitiators. Large-area (ca. 75 cm²) infrared LSCs were achieved with a high optical conversion efficiency of 3.1 % at a geometric factor of 10.     

Hydrochromic CsPbBr3 Nanocrystals for Anti-Counterfeiting

Hydrochromic materials that can reversibly change color upon water treatment have attracted much attention owing to their potential applications in diverse fields. Herein, for the first time, we report that space-confined CsPbBr₃ nanocrystals (NCs) are hydrochromic. When CsPbBr₃ NCs are loaded into a porous matrix, reversible transition between luminescent CsPbBr₃ and non-luminescent CsPb₂Br₅ can be achieved upon the exposure/removal of water. The potential applications of hydrochromic CsPbBr₃ NCs in anti-counterfeiting are demonstrated by using CsPbBr₃ NCs@mesoporous silica nanospheres (around 100 nm) as the starting material. Owing to the small particle size and negatively charged surface, the as-prepared particles can be laser-jet printed with high precision and high speed. We demonstrate the excellent stability over repeated transformation cycles without color fade. This new discovery may not only deepen the understanding of CsPbX₃, but also open a new way to design CsPbX₃ materials for new applications.     

Achiral Au(I) Cyclic Trinuclear Complexes with High-Efficiency Circularly Polarized Near-Infrared TADF

Realizing high photoluminescence quantum yield (PLQY) in the near-infrared (NIR) region is challenging and valuable for luminescent material, especially for thermally activated delay fluorescence (TADF) material. In this work, we report two achiral cyclic trinuclear Au(I) complexes, Au₃(4-Clpyrazolate)₃ and Au₃(4-Brpyrazolate)₃ (denoted as Cl−Au and Br−Au) , obtained through the reaction of 4-chloro-1H-pyrazole and 4-bromo-1H-pyrazole with Au(I) salts, respectively. Both Cl−Au and Br−Au exhibit TADF with high PLQY (>70 %) in the NIR I (700–900 nm) (λ_max = 720 nm) region, exceeding other NIR−TADF emitters in the solid state. Photophysical experiments and theoretical calculations confirmed the efficient NIR−TADF properties of Cl−Au and Br−Au were attributed to the small energy gap ΔE_(S1-T2) (S = singlet, T = triplet) and the large spin-orbital coupling induced by ligand-to-metal-metal charge transfer of molecular aggregations. In addition, both complexes crystallize in the achiral Pna2₁ space group (mm2 point group) and are circularly polarized light (CPL) active with maxima luminescent dissymmetry factor |g_lum| of 3.4 × 10⁻³ ( Cl−Au ) and 2.7 × 10⁻³ ( Br−Au ) for their crystalline powder samples, respectively. By using Cl−Au as the emitting ink, 3D-printed luminescent logos are fabricated, which own anti-counterfeiting functions due to its CPL behavior dependent on the crystallinity.     

Highly Luminescent One-Dimensional Organic–Inorganic Hybrid Double-Perovskite-Inspired Materials for Single-Component Warm White-Light-Emitting Diodes

Double perovskites (DPs) are one of the most promising candidates for developing white light-emitting diodes (WLEDs) owing to their intrinsic broadband emission from self-trapped excitons (STEs). Translation of three-dimensional (3D) DPs to one-dimensional (1D) analogues, which could break the octahedral tolerance factor limit, is so far remaining unexplored. Herein, by employing a fluorinated organic cation, we report a series of highly luminescent 1D DP-inspired materials, (DFPD)₂M^IInBr₆ (DFPD=4,4-difluoropiperidinium, M^I=K⁺ and Rb⁺). Highly efficient warm-white photoluminescence quantum yield of 92 % is achieved by doping 0.3 % Sb³⁺ in (DFPD)₂KInBr₆. Furthermore, single-component warm-WLEDs fabricated with (DFPD)₂KInBr₆:Sb yield a luminance of 300 cd/m², which is one of the best-performing lead-free metal-halides WLEDs reported so far. Our study expands the scope of In-based metal-halides from 3D to 1D, which exhibit superior optical performances and broad application prospects.     

Efficient and Stable Thin‐Film Luminescent Solar Concentrators Enabled by Near‐Infrared Emission Perovskite Nanocrystals

A novel triphenylphosphine (TPP) treatment strategy was developed to prepare the near‐infrared emission CsPbI₃ nanocrystal (NC)‐polymer composite thin‐film luminescent solar concentrators (LSCs) featuring high absolute photoluminescence quantum yield (PLQY), low reabsorption, and high stability. The PL emission of the LSCs is centered at about 700 nm with 99.4±0.4 % PLQY and narrow full width at half maximum (FWHM) of 75 meV (30 nm). Compared with LSCs prepared with classic CsPbI₃ NCs, the stability of the LSCs after TPP treatments has been greatly improved, even after long‐term (30 days) immersion in water and strong mercury‐lamp irradiation (50 mW cm^?2). Owing to the presence of lone‐pair electrons on the phosphorus atom, TPP is also used as a photoinitiator, with higher efficiency than other common photoinitiators. Large‐area (ca. 75 cm²) infrared LSCs were achieved with a high optical conversion efficiency of 3.1 % at a geometric factor of 10.     

Synergistic Enhancement Effects of Carbon Quantum Dots and Au Nanoclusters for Cathodic ECL and Non‐enzyme Detections of Glucose

In this study, we found that glucose enhance electrochemiluminescence (ECL) intensity of both Au nanoclusters (Au NCs) and carbon quantum dots (CQDs) with K₂S₂O₈ as the co‐reactants. The enhancing effects by Au NCs and CQDs were overlapped, enabling the detection of glucose. The increased ECL intensity of glucose was linear with the logarithm of concentrations of glucose in the range of 50 μM–3.0 mM, and the limit of detection is 20 μM. Anti‐interruption ability was achieved, and ascorbic acid, urea, and uric acid had little influence to glucose detection. This method realized the direct detection of glucose by enhancing ECL of Au NCs and CQDs, which was fast and economic, possessing potential applications for glucose detection in human serum.     

Facile Synthesis of Highly Emissive All-Inorganic Manganese Bromide Compounds with Perovskite-Related Structures for White LEDs

Lead-free all-inorganic halide materials with different Mn²⁺-based crystal structures (Cs₃MnBr₅ and CsMnBr₃) were obtained using a convenient synthetic method. Cs₃MnBr₅ had a bright green emission (522 nm), with a unique single-exponential lifetime (τ_avg = 236 µs) and a high photoluminescence quantum yield (82 ± 5%). A red emission was observed in the case of the CsMnBr₃ structure with a two-exponential fluorescence decay curve, and the lifetime was 1.418 µs (93%) and 18.328 µs (7%), respectively. By a judicious tuning of the synthetic conditions, a mixed phase of Cs₃MnBr₅/CsMnBr₃ was also produced that emitted white light, covering almost the entire visible spectrum. White-light-emitting diodes (WLEDs) with color coordinates (0.4269, 0.4955), a color temperature of (3773 K), and a color rendering index (68) were then fabricated using the as-prepared powder of mixed phases of Cs₃MnBr₅/CsMnBr₃ with a commercial UV LED chip (365 nm).     

Novel Composites of Graphitic‐phase Nitrogen Carbon/Lanthanide Coordination Polymers as White Light‐emitting Phosphor

Lanthanide coordination polymers (Ln‐CPs) are excellent candidates for designing white light materials due to their adjustable fluorescent characteristic by decorating organic ligands, changing metal centers and including guests. However, low quantum yield, weak blue emission, high prices and supply risks have hindered the application and developments of the pure Ln‐CPs materials. Herein, we have designed a new white color composite material capable of white light‐emission upon excitation at 338 nm, which fabricated by compositing a graphitic‐phase nitrogen carbon (g‐C₃N₄) treated with nitric acid and lanthanide‐based complexes, with the photoluminescencequantum yield (QY) in solid state reaching 11.7 %. WLEDs constructed by depositing the (g‐C₃N₄)_0.783/Eu_0.133/Tb_0.083‐dbpt [dbpt = 3‐(3,5‐dicarboxylphenyl)‐5‐(pyrazinyl)‐1H‐1,2,4‐triazole] composites on a commercial UV LED chip feature a CIE chromaticity coordinate at (0.33, 0.33), high color rendering index (CRI) of 94.6. Compared to conventional white light‐emission Ln‐CPs materials of La_0.928Eu_0.045Tb_0.027‐dbpt and La_0.896Eu_0.104‐dbpt reveals that (g‐C₃N₄)_0.783/Eu_0.133/Tb_0.083‐dbpt composites have higher QY and CRI values.     

Cancer Cell Imaging Using in Situ Generated Gold Nanoclusters

In situ generated fluorescent gold nanoclusters (Au‐NCs) are used for bio‐imaging of three human cancer cells, namely, lung (A549), breast (MCF7), and colon (HCT116), by confocal microscopy. The amount of Au‐NCs in non‐cancer cells (WI38 and MCF10A) is 20–40 times less than those in the corresponding cancer cells. The presence of a larger amount of glutathione (GSH) capped Au‐NCs in the cancer cell is ascribed to a higher glutathione level in cancer cells. The Au‐NCs exhibit fluorescence maxima at 490–530 nm inside the cancer cells. The fluorescence maxima and matrix‐assisted laser desorption ionization (MALDI) mass spectrometry suggest that the fluorescent Au‐NCs consist of GSH capped clusters with a core structure (Au_8‐13). Time‐resolved confocal microscopy indicates a nanosecond (1–3 ns) lifetime of the Au‐NCs inside the cells. This rules out the formation of aggregated Au–thiolate complexes, which typically exhibit microsecond (≈1000 ns) lifetimes. Fluorescence correlation spectroscopy (FCS) in live cells indicates that the size of the Au‐NCs is ≈1–2 nm. For in situ generation, we used a conjugate consisting of a room‐temperature ionic liquid (RTIL, [pmim][Br]) and HAuCl₄. Cytotoxicity studies indicate that the conjugate, [pmim][AuCl₄], is non‐toxic for both cancer and non‐cancer cells.