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Size reduction can generally enhance the surface reactivity of inorganic nanomaterials. The origin of this nano-effect has been ascribed to ultrasmall size, large specific surface area, or abundant defects, but the most intrinsic electronic-level principles are still not fully understood yet. By combining experimental explorations and mathematical modeling, herein we propose an electronic-level model to reveal the physicochemical nature of size-dependent nanomaterial surface reactivity. Experimentally, we reveal that competitive redistribution of surface atomic orbitals from extended energy band states into localized surface chemical bonds is the critical electronic process of surface chemical interactions, using H 2 O 2 -TiO 2 chemisorption as a model reaction. Theoretically, we define a concept, orbital potential ( G ), to describe the electronic feature determining the tendency of orbital redistribution, and deduce a mathematical model to reveal how size modulates surface reactivity. We expose the dual roles of size reduction in enhancing nanomaterial surface reactivity—inversely correlating to orbital potential and amplifying the effects of other structural factors on surface reactivity.

The linear relations between adsorption energies are one of the cornerstones of contemporary catalysis in view of the simplicity and predictive power of the computational models built upon them. Despite their extensive use, the exact nature of scaling relations is not yet fully understood, and a comprehensive theory of scaling relations is yet to be elaborated. So far, it is known that scalability is dictated by the degree of resemblance of the adsorbed species. In this work, density functional theory calculations show that CO and OH, two dissimilar species, scale or not depending on the surface facet where they adsorb at Pt alloys. This peculiar behavior arises from an interplay of ligand and geometric effects that can be used to modulate adsorption‐energy scalability. This study opens new possibilities in catalysis, as it shows that surface coordination is a versatile tool to either balance or unbalance the similarities among adsorbates at alloy surfaces. Currently, it is widely accepted that adsorption‐energy scaling relations exist or not depending on the similarity of the adsorbates. Here, we show that CO and OH scale linearly or not on Pt alloys depending on the coordination of the adsorption sites. Hence, ligand and geometric effects can be used to modulate scaling relations, thereby opening new possibilities in catalysis.

New surface coordination photocatalytic systems that are inspired by natural photosynthesis have significant potential to boost fuel denitrification. Despite this, the direct synthesis of efficient surface coordination photocatalysts remains a major challenge. Herein, it is verified that a coordination photocatalyst can be constructed by coupling Pd and CTAB-modified ZnIn2S4 semiconductors. The optimized Pd/ZnIn2S4 showed a superior degradation rate of 81% for fuel denitrification within 240 min, which was 2.25 times higher than that of ZnIn2S4. From the in situ FTIR and XPS spectra of 1% Pd/ZnIn2S4 before and after pyridine adsorption, we find that pyridine can be selectively adsorbed and form Zn⋅⋅⋅C-N or In⋅⋅⋅C-N on the surface of Pd/ZnIn2S4. Meanwhile, the superior electrical conductivity of Pd can be combined with ZnIn2S4 to promote photocatalytic denitrification. This work also explains the surface/interface coordination effect of metal/nanosheets at the molecular level, playing an important role in photocatalytic fuel denitrification.

Rare‐earth long persistent luminescence (LPL) materials with unique light‐storage properties show great promise for diverse applications. However, modifying the optical properties of such materials is extremely challenging due to their inherent characteristics. Here, we propose a coordination modification strategy that not only deepens the trap depth but also enhances the light‐capturing capability of rare‐earth LPL materials by introducing organic ligands as an antenna. Unlike previous single‐case demonstrations, this strategy is systematically validated across multiple LPL hosts with different afterglow colors, including green (SrAl 2 O 4 :Eu 2+ , Dy 3+ ), red (Sr 0.75 Ca 0.25 S:Eu 2+ ), and blue (SrSiO 3 :Eu 2+ , Dy 3+ ). Experimental results demonstrate that the afterglow intensity, brightness, and duration of the organic–inorganic hybrid LPL materials have been significantly enhanced compared to the original LPL materials. Based on this performance breakthrough, we further demonstrate the application potential of these materials in diverse scenarios, including flexible displays, intelligent sensors, and multi‐level information encryption. This work not only provides an efficient method for enhancing the performance of multi‐color long persistent luminescence materials but also offers new design insights for developing novel organic–inorganic hybrid luminescent systems.

Long‐persistent luminescent (LPL) materials have attracted considerable research interest due to their extensive applications and outstanding afterglow performance. However, the performance of red LPL materials lags behind that of green and blue materials. Therefore, it is crucial to explore novel red LPL materials. This study introduces a straightforward and viable strategy for organic–inorganic hybrids, wherein the organic ligand 1,3,6,8‐Tetrakis(4‐carboxyphenyl)pyrene (TCPP) is coordinated to the surface of a red persistent phosphor Sr0.75Ca0.25S:Eu2+ (R) through a one‐step method. TCPP serves as an antenna, facilitating the transfer of absorbed light energy to R via triplet energy transfer (TET). Notably, the initial afterglow intensity and luminance of R increase by twofold and onefold, respectively, and the afterglow duration extends from 9 to 17 min. Furthermore, this study involves the preparation of a highly flexible film by mixing R@TCPP with high‐density polyethylene (HDPE) to create a sound‐controlled afterglow lamp. This innovative approach holds promising application prospects in flexible large‐area luminescence, flexible wearables, and low‐vision lighting. Outstanding red long‐persistent luminescence materials are achieved through surface coordination interactions between organic ligands and inorganic phosphors. Remarkably, the afterglow performance of this material experienced significant enhancement due to the interplay of triplet energy transfer and the trap effect.

The inherent hydroxide‐rich (OH⁻) environment in alkaline media facilitates the two‐electron oxygen reduction reaction (2e−ORR). However, the strong interaction between alkali metal cations and solvated water molecules significantly reduces the connectivity of the hydrogen bond network within the alkaline electric double layer, thereby severely impeding rapid proton transport at the electrode surface. Herein, we rationally designed ZnO with oxygen vacancies‐driven [Fe(CN)6]3− coordination (denoted as Fe(CN)6‐ZnO‐VO) as an efficient 2e−ORR catalyst for H2O2 electrosynthesis. We demonstrate that the locally coordinated [Fe(CN)6]3− establishes pathways for rapid proton transfer at the electrode surface by forming a hydrogen bond network with interfacial water molecules. Concurrently, this configuration significantly reduces the energy barrier of the *OOH intermediate. These synergistic effects collectively optimize the electrocatalytic performance for H2O2 production under alkaline conditions. As expected, the Fe(CN)6‐ZnO‐VO delivers a significantly increased current density of 130 mA cm−2 that is much higher than ZnO (32 mA cm−2), as well as a superior H2O2 production rate of 9.41 mol gcat−1 h−1 and a high faradaic efficiency of exceeds 90%. Our study highlights the crucial role of interfacial hydrogen‐bonding connectivity and provides theoretical and technical guidance for developing reliable strategies to enhance the electrocatalytic properties of 2e−ORR.

Monodisperse silica nanoparticles were synthesised by the well-known Stober protocol, then dispersed in acetonitrile (ACN) and subsequently added to a bisacetonitrile gold(I) coordination complex ([Au(MeCN) 2 ] + ) in ACN. The silica hydroxyl groups were deprotonated in the presence of ACN, generating a formal negative charge on the siloxy groups. This allowed the [Au(MeCN) 2 ] + complex to undergo ligand exchange with the silica nanoparticles and form a surface coordination complex with reduction to metallic gold (Au 0 ) proceeding by an inner sphere mechanism. The residual [Au(MeCN) 2 ] + complex was allowed to react with water, disproportionating into Au 0 and Au(III), respectively, with the Au 0 adding to the reduced gold already bound on the silica surface. The so-formed metallic gold seed surface was found to be suitable for the conventional reduction of Au(III) to Au 0 by ascorbic acid (ASC). This process generated a thin and uniform gold coating on the silica nanoparticles. The silica NPs batches synthesised were in a size range from 45 to 460 nm. Of these silica NP batches, the size range from 400 to 480 nm were used for the gold-coating experiments.

Area-selective atomic layer deposition (AS-ALD) is a technique utilized for the fabrication of patterned thin films in the semiconductor industry due to its capability to produce uniform and conformal structures with control over thickness at the atomic scale level. In AS-ALD, surfaces are functionalized such that only specific locations exhibit ALD growth, thus leading to spatial selectivity. Self-assembled monolayers (SAMs) are commonly used as ALD inhibiting agents for AS-ALD. However, the choice of organic molecules as viable options for AS-ALD remains limited and the precise effects of ALD nucleation and exposure to ALD conditions on the structure of SAMs is yet to be fully understood. In this work, we investigate the potential of small molecule carboxylates as ALD inhibitors, namely benzoic acid and two of its derivatives, 4-trifluoromethyl benzoic acid (TBA), and 3,5-Bis (trifluoromethyl)benzoic acid (BTBA) and demonstrate that monolayers of all three molecules are viable options for applications in ALD blocking. We find that the fluorinated SAMs are better ALD inhibitors; however, this property arises not from the hydrophobicity but the coordination chemistry of the SAM. Using nanoscale infrared spectroscopy, we probe the buried monolayer interface to demonstrate that the distribution of carboxylate coordination states and their evolution is correlated with ALD growth, highlighting the importance of the interfacial chemistry in optimizing and assessing ALD inhibitors.

We chemically modified the surface of kaolinite with nanoclusters of aluminum hydroxo cations. We have determined their composition and sizes. We have used IR spectroscopy to establish the interaction between the carbonyl and β-diketone groups of fulvic and humic acids with the Lewis acid sites: coordination unsaturated Al3+ cations of the Al13 nanoclusters. We have obtained spectral evidence for hydrogen bond formation between the carboxyl groups of fulvic acid and the hydroxyl groups of the aluminum hydroxo cations.

Boron oxide has been added to commercial silicate glasses for many years to aid in lowering melting temperatures, lowering thermal expansion, and controlling chemical durability. The fact that simple borate glasses have rather high thermal expansion and low chemical durability attests to the unique influence of boron oxide additions upon the properties of silicate glasses. However, the impact of boron oxide additions upon surface properties of multicomponent borosilicates such as adsorption and reactivity is not yet well understood. In particular, the presence of multiple coordination states for boron is expected to introduce adsorption sites with different acidic or basic behavior, but their existence is yet unproven. To investigate these effects, multicomponent sodium aluminosilicate glasses have been prepared with varying sodium and boron concentrations and drawn into moderately high-surface-area continuous filament fibers. A relatively new technique, boron K-edge Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy is applied to study the local boron coordination at fracture and melt-derived fiber surfaces of these glasses. This structural information is combined with surface compositional information by X-ray Photoelectron Spectroscopy (XPS) to characterize the local atomic structure of boron at the as-formed glass surface. Finally, this information is used to interpret the adsorptivity of these as-formed and leached surfaces toward short-chain alcohol molecules through a new Inverse Gas Chromatography—Temperature Programmed Desorption (IGC-TPD) experiment. The results clearly show that boron additions to alkali-free glass surfaces introduce a unique adsorption site which is not present on boron-free glass surfaces and is easily removed by leaching in acidic solutions.