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The excited state intramolecular proton transfer (ESIPT) reaction is a well-studied photo reaction, based on this mechanism, many high-performance organic chromophores can be selected. It is widely acknowledged that the 2-(2'-hydroxyphenyl)benzazole (HBX) derivatives undergo the ESIPT process. This work mainly uses DFT and TDDFT methods to clarify the effects of oxygen family substituted elements on excited states for HBX derivatives. First, we probe into the molecular structures of HBX derivatives (HBX-O, HBX-S and HBX-Se) and explore their infrared (IR) vibrational behaviours. The results confirm that light excitation in S1 state enhances the hydrogen bonds of HBX dyes. Additionally, analysis of the frontier molecular orbitals shows that charge redistribution promotes the ESIPT process. This article provides a detailed explanation of the excited state reaction behaviours of three HBX dyes and demonstrates that substitution effects regulate the ESIPT processes of these dyes. This finding will contribute to the development of new photo-reactive substances in the future. [ABSTRACT FROM AUTHOR]

Ni‐based electrocatalysts are considered to be significantly promising candidates for electrocatalytic urea oxidation reaction (UOR). However, their UOR activity and stability are severely enslaved by the inevitable Ni group self‐oxidation phenomenon. In this study, the glassy state NiFe LDH with uniform Cu dopant (Cu‐NiFe LDH) by a simple sol–gel strategy is successfully synthesized. When served as the UOR catalyst, Cu‐NiFe LDH required a 123 mV lower potential for UOR at both 10 and 100 mA cm−2 in comparison with the conventional anodic OER. It can also operate steadily for more than 300 h at 10 mA cm−2. The in‐depth investigation reveals that Cu incorporation can optimize the local electronic structure of Ni species to induce high‐valent Ni sites. The high‐valent Ni sites would act as the active center during the proposed energetically favorable UOR route, which directly reacts on the high‐valent Ni sites without self‐oxidation inducing the formation of NiOOH species, resulting in a boosted electrocatalytic UOR activity and stability. [ABSTRACT FROM AUTHOR]

The utilization of heterostructured electrodes offers an effective approach to boost the energy density of supercapacitors without sacrificing their power density. However, the adoption of such materials is frequently impeded by sluggish reaction kinetics. Herein, an island‐like CoNi2S4@NiCo‐layered double hydroxide/biomass carbon (CoNi2S4@NiCo‐LDH/BC) heterostructure is synthesized by embedding CoNi2S4 in the interlayer of NiCo‐LDH nanosheets on BC through a partial in situ sulfidation process. Theoretical and experimental analyses indicate that this unique structural configuration lowers transport barriers and enhances ion adsorption capacity, leading to a significant improvement in ion/electron reaction kinetics. In addition, the embedded structural design effectively alleviates the significant volume expansion during charge–discharge process, while the robust BC framework prevents electrode degradation, thereby enhancing stability. These advantages enable the developed electrode material to achieve a high specific capacity (1655.75 C g−1 at 1 A g−1) and an extended cycle life (86.82% capacity retention after 10 000 cycles). Significantly, the assembled hybrid supercapacitor CoNi2S4@NiCo‐LDH/BC// activated carbon demonstrates a remarkable energy density of 95.57 Wh kg−1 at 866.61 W kg−1 and exceptional cycling stability, maintaining 95.16% capacity after 10 000 cycles. This research offers an effective strategy to promote ion/charge transfer and adsorption capacity of heterostructure and provides a new approach to the development of advanced supercapacitor electrodes. [ABSTRACT FROM AUTHOR]

Advancing and deploying the FeNi-based catalyst, the state-of-the-art pre-electrocatalysts, for oxygen evolution reactions (OER) still suffer from unclear chemical state correlation to the catalytic ability, as evidenced by the variedly reported performance for the different FeNi structures. Herein, we contributed the phase and redox chemical states tuning of FeNi oxides by the surface microenvironment regulation for the OER catalysis that was realized by the urea-assisted pyrolysis and molybdenum-doping technique by integrating molybdenum into the iron–nickel metal-organic precursor. Driven by the complicated and compromised atmosphere, namely, the oxidation state driven by the Mo doping and reduction ability induced by the urea-assisted pyrolysis, could transfer confined FeNi oxides to hybrid phases of Fe2O3 and FeNi3 alloy, and the resultant compromised chemical states by the charge redistribution imparted very high electrocatalytic performance for OER compared with the control samples. The in-situ Raman spectroscopy and post-XPS analysis confirmed the facile Fe/Ni oxyhydroxide active phase formation resulting from the proper phase and chemical states, and theoretical analysis disclosed the microenvironment regulation resulting in the charge redistribution forming the electron accumulation and depletion sites to accelerate the oxygen-species to oxyhydroxide-species transformation and enhance the electronic state density near the Fermi level by significantly reducing the energy barrier. The work not only showed the importance of surface chemical state tunning that can basically answer the varied performance of FeNi catalysts but also revealed an effective approach for fine-tuning their catalytic properties. [ABSTRACT FROM AUTHOR]

Inspired by the remarkable photochemical and photophysical properties of novel 2-(2'-hydroxyphenyl)benzothiazole (HBT) derivatives that could be potentially applied across various disciplines, in this work, effects of atomic electronegativity of chalcogen elements on excited state hydrogen bond effects and excited state intramolecular proton transfer (ESIPT) reaction of the biphenyl-modified HBT derivatives (i.e. HBT-HH-O, HBT-HH-S and HBT-HH-Se) are focused. By comparing the structural changes and infrared (IR) vibrational spectra of the HBT-HH fluorophores in toluene solvent, combined with the preliminary detection of hydrogen bond interaction by core-valence bifurcation (CVB) index, we can conclude that the hydrogen bond could be strengthened in S1 state, which is favourable for the occurrence of ESIPT reactions. The charge recombination behaviour of hydrogen bond induced by photoexcitation also further illustrates this point. Via constructing potential energy curves (PECs) based on restrictive optimisation and searching transition state (TS) form, we confirm the variations of atomic electronegativity of chalcogen have the regulatory effect on the ESIPT behaviour for HBT-HH derivatives, that is, the lower the atomic electronegativity is more conducive to the ESIPT reaction. [ABSTRACT FROM AUTHOR]

Solution‐processed 2D materials hold promise for their scalable applications. However, the random, fragmented nature of the solution‐processed nanoflakes and the poor percolative conduction through their discrete networks limit the performance of the enabled devices. To overcome the problem, conduction modulation of the solution‐processed 2D materials is reported via Stark effect. Using liquid‐phase exfoliated molybdenum disulfide (MoS2) as an example, nonlinear conduction switching with a ratio of >105 is demonstrated by the local fields from the interfacial ferroelectric P(VDF‐TrFE). Through density‐functional theory calculations and in situ Raman scattering and photoluminescence spectroscopic analysis, the modulation is understood to arise from a charge redistribution in the solution‐processed MoS2. Beyond MoS2, the modulation may be shown effective for the other solution‐processed 2D materials and low‐dimensional materials. The modulation can open their electronic device applications, for instance, thin‐film nonlinear electronics and non‐volatile memories. [ABSTRACT FROM AUTHOR]

The FePc-based covalent organic polymers (COP FePc) polymerized in situ on the functionalized multiwalled carbon nanotubes (R-MWCNT) were synthesized (COP FePc /R-MWCNT, R = COOH, OH or NH 2) for ORR under pH-universal conditions. The carbon nanotubes with electron-withdrawing or electron-donating groups induce charge redistribution around the active center Fe, tuning the ORR activity. The COP FePc /COOH-MWCNT catalyst exhibited an impressive ORR activity with half-wave potentials of 0.92, 0.78, and 0.72 V in alkaline, acidic, and neutral electrolytes, respectively. [Display omitted] Iron phthalocyanine (FePc) is an attractive nonprecious metal candidate for electrocatalytic oxygen reduction reaction (ORR). However, its low catalytic performance under acidic and neutral conditions limits its practical application. Herein, the FePc-based covalent organic polymers (COP FePc) polymerized in situ on the functionalized multiwalled carbon nanotubes (R-MWCNT) containing different electron-withdrawing or electron-donating groups (COP FePc /R-MWCNT, R = COOH, OH or NH 2) were synthesized for ORR. Among them, COP FePc /COOH-MWCNT exhibited the best ORR performance under pH-universal conditions (acidic, neutral, and alkaline). Density-functional theory (DFT) calculations demonstrate that the electron-withdrawing or electron-donating effect of the functional groups in COP FePc /R-MWCNT causes charge redistribution of the active center Fe. The COOH functional group with an electron-withdrawing ability shifts the d -band center of Fe away from the Fermi energy level and reduces the binding strength of oxygen-containing intermediates, accelerating the ORR kinetics and optimizing the catalytic activity. [ABSTRACT FROM AUTHOR]

Electrocatalytic CO2‐to‐formate conversion is considered an economically viable process. In general, Zn‐based nanomaterials are well‐known to be highly efficient electrocatalysts for the conversion of CO2 to CO, but seldom do they exhibit excellent selectivity toward formate. In this article, we demonstrate that a heterointerface catalyst ZnO/ZnSnO3 with nanosheet morphology shows enhanced selectivity with a maximum Faradaic efficiency (FE) of 86% at −0.9 V versus reversible hydrogen electrode and larger current density for the conversion of CO2 to formate than pristine ZnO and ZnSnO3. In particular, the FEs of the C1 products (CO + HCOO−) exceed 98% over the potential window. The experimental measurements combined with theoretical calculations revealed that the ZnO in ZnO/ZnSnO3 heterojunction delivers the valence electron depletion and accordingly optimizes Zn d‐band center, which results in moderate Zn–O hybridization of HCOO* and weakened Zn–C hybridization of competing COOH*, thus greatly boosting the HCOOH generation. Our study highlights the importance of charge redistribution in catalysts on the selectivity of electrochemical CO2 reduction. [ABSTRACT FROM AUTHOR]

Abstract Solution‐processed 2D materials hold promise for their scalable applications. However, the random, fragmented nature of the solution‐processed nanoflakes and the poor percolative conduction through their discrete networks limit the performance of the enabled devices. To overcome the problem, conduction modulation of the solution‐processed 2D materials is reported via Stark effect. Using liquid‐phase exfoliated molybdenum disulfide (MoS2) as an example, nonlinear conduction switching with a ratio of >105 is demonstrated by the local fields from the interfacial ferroelectric P(VDF‐TrFE). Through density‐functional theory calculations and in situ Raman scattering and photoluminescence spectroscopic analysis, the modulation is understood to arise from a charge redistribution in the solution‐processed MoS2. Beyond MoS2, the modulation may be shown effective for the other solution‐processed 2D materials and low‐dimensional materials. The modulation can open their electronic device applications, for instance, thin‐film nonlinear electronics and non‐volatile memories.

Abstract Electrocatalytic CO2‐to‐formate conversion is considered an economically viable process. In general, Zn‐based nanomaterials are well‐known to be highly efficient electrocatalysts for the conversion of CO2 to CO, but seldom do they exhibit excellent selectivity toward formate. In this article, we demonstrate that a heterointerface catalyst ZnO/ZnSnO3 with nanosheet morphology shows enhanced selectivity with a maximum Faradaic efficiency (FE) of 86% at −0.9 V versus reversible hydrogen electrode and larger current density for the conversion of CO2 to formate than pristine ZnO and ZnSnO3. In particular, the FEs of the C1 products (CO + HCOO−) exceed 98% over the potential window. The experimental measurements combined with theoretical calculations revealed that the ZnO in ZnO/ZnSnO3 heterojunction delivers the valence electron depletion and accordingly optimizes Zn d‐band center, which results in moderate Zn–O hybridization of HCOO* and weakened Zn–C hybridization of competing COOH*, thus greatly boosting the HCOOH generation. Our study highlights the importance of charge redistribution in catalysts on the selectivity of electrochemical CO2 reduction.

Inspired by its potential applications of organic luminescence and fluorescence probe materials for 2-(2′-hydroxyphenyl)benzazoles (HBX) derivatives, this study mainly investigates the excited-state behaviours of a novel 2-benzooxazol-2-yl-6-thiophen-2-yl-phenol (BYTYP) fluorophore. Theoretical exploration has been conducted on the solvent-dependent interactions of excited-state intramolecular hydrogen bonding and the process of excited-state intramolecular proton transfer (ESIPT) for BYTYP. By combining optimised geometrical modifications, infrared (IR) vibrational spectra and the core-valence bifurcation (CVB) index, hydrogen bonding strengthening can be confirmed. Predicting the bond energy (EHB), we assert that nonpolar solvents are more conducive to enhancing hydrogen bonding interactions. The ESIPT tendency of BYTYP is further elucidated by charge reorganisation resulting from photoexcitation. By exploring potential energy surfaces (PESs) and identifying transition states (TS), we have uncovered the solvent-polarity-controlled ESIPT behaviours. We hope these insights into excited-state dynamics will facilitate the design and development of novel fluorescent sensors in future. [ABSTRACT FROM AUTHOR]

Urea oxidation reactions (UOR) coupled with hydrogen generation simultaneously is a promising strategy for developing sustainable energy conversion technologies, but the complexity of urea oxidation dynamics and the high coupling hydrogen evolution potential through a single catalyst limit its industrial application. Herein, a kind of novel bifunctional NiPx/MoS2/CC hybrid catalyst can be fabricated via a hydrothermal method followed by a facile in‐situ electrodeposition process. The prepared NiPx/MoS2/CC catalyst exhibits an overpotential of only 88 mV at 10 mA cm−2 for HER while the potential for UOR was only 1.36 V at 10 mA cm−2. Further, the urea electrolytic cell assembled of the NiPx/MoS2/CC catalyst displays low potential (1.45 V@10 mA cm−2) and better long‐term durability. The improved electrocatalytic performances are mainly attributed to the intimately coupled interface between NiPx and MoS2, enormously improving the conductivity and increasing the heterogenous interface active area. Additionally, the closely incorporated heterogeneous interfaces trigger charge redistribution, which induces the fast electron transfer from the NiPx to MoS2. In a word, the present results can provide a feasible research strategy for design advanced multi‐functional catalysts via interfacial engineering for clean energy conversion applications. [ABSTRACT FROM AUTHOR]

Pt clusters assembled on Mo doped NiO x nanosheet arrays (Pt/Mo-NiO x) is prepared on the surface of NiMo foam (NMF) by an efficient light-driven redox reaction. The Pt/Mo-NiO x /NMF electrode exhibits outstanding alkaline HER activity with low overpotential of only 62 mV to achieve the current density of 100 mA cm−2. [Display omitted] Designing cost-effective alkaline hydrogen evolution reaction (HER) catalysts with high water dissociation ability, enhanced hydroxyl transfer rate and optimized hydrogen adsorption free energy (ΔG H*) by a time and energy efficient strategy is pivotal, but still challenging for alkaline water electrolysis. Herein, Pt/Mo-NiO x hybrid consisting of Pt clusters assembled on Mo-doped NiO x nanosheet arrays is prepared on the surface of raw NiMo foam (NMF) by a light-driven strategy to address this challenge. Benefitting from the electronic interaction between Mo-NiO x and Pt, the Pt/Mo-NiO x composite owns optimized ΔG H* and is beneficial for accelerating water dissociation and hydroxyl transfer. As a result, the optimized Pt/Mo-NiO x /NMF electrode displays an exceptional alkaline HER activity with a low overpotential of 62 mV to obtain 100 mA cm−2 and a high Pt mass activity (13.2 times as high as that of commercial 20 wt% Pt/C). Furthermore, the assembled two-electrode cell of Pt/Mo-NiO x /NMF||NiFe-LDH/NF requires a voltage of only 1.549 V to deliver 100 mA cm−2, along with negligible activity decay after 70 h stability test. The present study provides a promising strategy for exploiting high-performance electrocatalysts towards alkaline HER. [ABSTRACT FROM AUTHOR]

Transition metal selenides (TMSs) have been widely believed as promising anode materials for sodium-ion batteries (SIBs). Element doping is a promising but ambiguous strategy to further enhance sodium storage performance due to the complexity of doping conditions and the sensitivity of the selenization process. Herein, tellurium (Te) is selected to fabricate Te-doped nickel cobalt selenide (Te-NiCoSe) using a melting method. Besides the common merit of expanding the interplanar space of NiCoSe, the melted Te can also result in a "size splitting effect" to decrease the particle size of bulk NiCoSe, exposing more surface active sites and accelerating the intercalation/deintercalation reaction kinetics. In addition, the introduction of Te can also inhibit the "reduction effect" of the selenization process induced by high temperature, which results in the charge redistribution of NiCoSe, stabilizing the electronic structure. As a result, the fabricated Te-NiCoSe exhibits a high reversible capacity of 448.7 mA h g–1 at 1 A g–1, a superior rate capacity of 324.9 mA h g–1 at 30 A g–1, and an outstanding capacity retention rate of 88.5% after 1000 cycles at 20 A g–1. [ABSTRACT FROM AUTHOR]

The serious shuttle effect and sluggish reaction kinetics intrinsically handicap the practical application of Li-S batteries. Herein, a unique 3D hierarchically porous Mott-Schottky electrocatalyst composed of W2C quantum dots (QD) spatially confined in nitrogen-doped graphene microspheres (NGM) is proposed for regulating the kinetics of sulfur electrochemistry. Experimental and theoretical results disclose a spontaneous charge rearrangement and induce built-in electric field across the W2C QD/NGM heterojunction interface, contributing to reduced energy barrier for both polysulfides reduction and Li2S oxidation during entitle discharge/charge processes. Furthermore, the ultrasmall W2C QD with high electrocatalytic activity and superior conductivity can promote the conversion of S species, while the hierarchically porous microspheres assembled from wrinkled graphene nanosheets not only can efficiently inhibit the polysulfides shuttling via multiple spatial confinement, but also provide abundant inner space for stable reservation of active S, highly conductive networks, and maintain the structural integrity of cathode during consecutive cycling. Consequently, Li-S batteries employed with the designed W2C QD/NGM-based cathode exhibit outstanding electrochemical properties even at a high sulfur loading. The superior performance combined with the simplicity of the synthesis process represents a promising strategy for the rational design of advanced electrocatalyst for energy applications. [ABSTRACT FROM AUTHOR]

Objective: A theoretical atomic‐electronegativity‐controlled photo‐induced hydrogen bonding interactions and intramolecular proton transfer mechanism is presented for 4'‐dimethylamino‐flavonol derivatives. Methods: Density functional theory and time‐dependent density functional theory are applied to explore all the electronic properties coupling with B3LYP functional as well as TZVP basis set. Results: Photo‐induced hydrogen bonding enhancing promotes the ESIPT behavior for 4'‐dimethylamino‐flavonol derivatives, which could be affected by atomic electronegativity. Conclusion: Hydrogen bonding strengthening coupling with intramolecular charge transfer reveal the ESIPT tendency, which could be regulated by substituted atomic electronegativities for 4DF derivatives. [ABSTRACT FROM AUTHOR]

In this work, we mainly focus on probing into the effects of atomic electronegativity on photo‐induced hydrogen bond (i.e., O–H···N) effects and excited state intramolecular proton transfer (ESIPT) processes for a novel fluorescent chemical probe ONIP derivatives (i.e., ONIP‐O, ONIP‐S, and ONIP‐Se). First, insights into optimized structural geometries and related infrared vibrational spectra, we clarify that the hydrogen bond O–H···N interaction could be strengthened via photoexcitation. Further, via predicting hydrogen bonding energy EHB, we quantificationally present that the S1‐state hydrogen bonding strengthening behavior should be more distinct with lower atomic electronegativity. When it comes to vertical photo‐induced excitation, the intramolecular charge transfer process happens and the charge redistribution plays roles in promoting ESIPT behavior. It is worth mentioning the energy gap between highest occupied molecular orbital and lowest unoccupied molecular orbital show that low atomic electronegativity should be more favorable to ESIPT process. Finally, based on the restricted optimization method, we construct the potential energy curves along with hydrogen bond wire for ONIP‐O, ONIP‐S, and ONIP‐Se. By exploring the conformation of potential energy curves and potential energy barriers, we disclose the detailed atomic‐electronegativity‐controlled ESIPT dynamical behaviors for ONIP system. [ABSTRACT FROM AUTHOR]

In the light of potential applications for detecting cysteine in vitro and in vivo, 2‐([1, 1′‐biphenyl]‐4‐yl)‐3‐hydroxy‐4H‐chromen‐4‐one (B‐bph‐fla‐OH) is explored about its excited state behaviors. Solvent‐polarity‐related photo‐induced hydrogen bond of B‐bph‐fla‐OH indicates nonpolar aprotic solvents largely enhance S1‐state hydrogen bonding interactions. Charge reorganization stemming from photoexcitation and polarity‐dependent energy gap between HOMO and LUMO orbitals further reveals the excited state intramolecular proton transfer (ESIPT) tendency. Insights into potential energy curves along ESIPT paths in solvents with different polarities and emission spectral behaviors of proton‐transfer tautomer, we present solvent polarity could harness the excited state behaviors for B‐bph‐fla‐OH system. [ABSTRACT FROM AUTHOR]

Van der Waals (vdW) heterostructures are promising for next-generation two-dimensional electronic and optoelectronic devices. The performance of such devices is completely determined by the properties of the interface. However, due to a lack of contamination-free fabrication techniques, obtaining an ideal interface is still a challenge. Meanwhile, the efficiency of photodetectors and solar cells is highly dependent on the charge separation on the interface. Thus, the questions on the effect of interfacial conditions on a contact type, charge redistribution, and photoluminescence still exist. In this work, the effect of interfacial conditions on the optical and electronic properties of MoSe2/Au heterostructure is studied. The tip of an atomic force microscope is used to clean the interface and change interfacial conditions. Kelvin probe microscopy revealed that the work function of the MoSe2 monolayer increases by 40 meV, the bilayer by 28 meV, and the trilayer by 12 meV due to charge redistribution after the cleaning. Micro-photoluminescence (μ-PL) investigation shows that the cleaning leads to the fall of photoluminescence intensity of about 75% for a monolayer and 60% for a bilayer. Raman spectroscopy indicates that the cleaning procedure did not damage the MoSe2 flake. It is shown that the presence of interfacial contamination in vdW heterostructures severely affects its electronic and optical properties. The results of the work are of great importance to vdW device fabrication. [ABSTRACT FROM AUTHOR]

MoO 3-x nanowires containing asymmetric defects were successfully prepared. Given the charge redistribution on the atomic and nanoscale, the optimal nitrogen fixation rate reached 200.35 ⋅g cat −1h−1. [Display omitted] Photocatalytic ammonia synthesis technology has become one of the effective methods to replace the Haber method for nitrogen fixation in the future for its low energy consumption and green environment. However, limited by the weak adsorption/activation ability of N 2 molecules at the photocatalyst interface, the efficient nitrogen fixation still remains a daunting job. Defect-induced charge redistribution as a catalytic site for N 2 molecules is the most prominent strategy to enhance the adsorption/activation of N 2 molecules at the interface of catalysts. In this study, MoO 3-x nanowires containing asymmetric defects were prepared by a one-step hydrothermal method via using glycine as a defect inducer. It is shown that at the atomic scale, the defect-induced charge reconfiguration can significantly improve the nitrogen adsorption and activation capacity and enhance the nitrogen fixation capacity; at the nanoscale, the charge redistribution induced by asymmetric defects effectively improved the photogenerated charge separation. Given the charge redistribution on the atomic and nanoscale of MoO 3-x nanowires, the optimal nitrogen fixation rate of MoO 3-x reached 200.35 µmol g−1h−1. [ABSTRACT FROM AUTHOR]

Inspired by the excellent photochemical properties of 3‐hydroxyflavone and its derivatives, in this work, the novel 2‐phenyl‐3‐hydroxybenzo[g]quinolone (2P3HBQ) fluorophore is explored about its photo‐induced behaviors. By investigating the photoexcitation characteristics in different solvents as well as the substituted atomic electronegativity (O→S→Se), the solvent‐polarity‐related and atomic‐electronegativity‐dependent photo‐induced hydrogen bond of 2P3HBQ and its derivatives (2P3HBQ‐O, 2P3HBQ‐S and 2P3HBQ‐Se) indicates the S1‐state hydrogen bonding interactions could be enhanced. Particularly, the nonpolar solvent environment and low atomic electronegativity substitution play large roles in strengthening hydrogen bonding effects. Charge reorganization stemming from photoexcitation, strengthening excited state hydrogen bond effects, and the intramolecular charge transfer (ICT) via frontier molecular orbitals (MOs) further reveals the excited state intramolecular proton transfer (ESIPT) tendency. Via the manner of constructing potential energy curves (PECs) with restricted optimization, we elaborate and reveal the novel solvent‐polarity‐regulated and the atomic‐electronegativity‐controlled ESIPT dynamical behaviors. [ABSTRACT FROM AUTHOR]

The development of efficiently active and stable bifunctional noble‐metal‐based electrocatalysts toward overall water splitting is urgent and challenging. In this work, a rutile‐structured ruthenium‐zinc solid solution oxide with oxygen vacancies (Ru0.85Zn0.15O2‐δ) is developed by a simple molten salt method. With naturally abundant edges of ultrasmall nanoparticles clusters, Ru0.85Zn0.15O2‐δ requires ultralow overpotentials, 190 mV for acidic oxygen evolution reaction (OER) and 14 mV for alkaline hydrogen evolution reaction (HER), to reach 10 mA cm−2. Moreover, it shows superior activity and durability for overall water splitting in different electrolytes. Experimental characterizations and density functional theory calculations indicate that the incorporation of Zn and oxygen vacancies can optimize the electronic structure of RuO2 by charge redistribution, which dramatically suppresses the generation of soluble Rux>4 and allows optimized adsorption energies of oxygen intermediates for OER. Meanwhile, the incorporation of Zn can distort local structure to activate the dangling O atoms on the distorted Ru0.85Zn0.15O2‐δ as proton acceptors, which firmly bonds the H atom in H2O* to stabilize the H2O and considerably improves the HER activity. [ABSTRACT FROM AUTHOR]

The performance optimization of isolated atomically dispersed metal active sites is critical but challenging. Here, TiO2@Fe species-N-C catalysts with Fe atomic clusters (ACs) and satellite Fe-N4 active sites were fabricated to initiate peroxymonosulfate (PMS) oxidation reaction. The AC-induced charge redistribution of single atoms (SAs) was verified, thus strengthening the interaction between SAs and PMS. In detail, the incorporation of ACs optimized the HSO5 -oxidation and SO5 ·-desorption steps, accelerating the reaction progress. As a result, the Vis/TiFeAS/PMS system rapidly eliminated 90.81% of 45 mg/L tetracycline (TC) in 10 min. The reaction process characterization suggested that PMS as an electron donor would transfer electron to Fe species in TiFeAS, generating 1O2. Subsequently, the hVB + can induce the generation of electron-deficient Fe species, promoting the reaction circulation. This work provides a strategy to construct catalysts with multiple atom assembly-enabled composite active sites for high-efficiency PMS-based advanced oxidation processes (AOPs). [ABSTRACT FROM AUTHOR]

Inspired by the excellent photochemical properties of hydroxybenzo[h]quinoline and its derivatives, in this work, the novel electron withdrawing nitro substituted HBQ (i.e., NHBQ) fluorophore is explored about its photo-induced behaviors. By investigating the photoexcitation characteristics in different solvents, the solvent-polarity-related photo-induced hydrogen bond of NHBQ indicates polar aprotic solvents largely enhance S1-state hydrogen bond interactions. Charge reorganization stemming from photoexcitation, strengthening excited state hydrogen bond effects, and the polarity-dependent energy gap of frontier molecular orbitals further reveals the excited state intramolecular proton transfer (ESIPT) tendency. Insights into potential energy curves along ESIPT paths in solvents with different polarities, we present that solvent polarity could harness the ESIPT behavior for NHBQ compound. [ABSTRACT FROM AUTHOR]

[Display omitted] • Photo-induced excited state dual hydrogen bonding strengthening facilitates ESDPT tendency. • Constructed S 1 -state PESs and potential barriers reveal the stepwise ESDPT mechanism. • We elucidate specific atomic-electronegativity-dependent ESDPT behaviors for Oxa derivatives. In view of the distinguished photochemical and photobiological characteristics of oxazolinyl-substituted hydroxyfluorene and its derivatives, herein, we mainly focus on probing into excited state behaviors of the novel 9,9-dimethyl-3,6-dihydroxy-2,7-bis(4,5-dihydro-4,4-dimethyl-2-oxazolyl) fluorene (Oxa-OH) derivatives. In light of the significant effects resulting from substituting oxygen elements, three Oxa-OH derivatives (i.e., Oxa-OO, Oxa-SS and Oxa-SeSe fluorophores) are considered in this work. For these three different fluorophores, we detangle the effects of atomic electronegativity and charge recombination related to oxygen elements in excited state double proton transfer (ESDPT) processes. Because of the low potential energy barriers, we confirm the ESDPT happens by the sequential type. Based on heterosubstituted Oxa-OS and Oxa-OSe compounds, we further verify the chalcogen atomic-electronegativity-regulated stepwise ESDPT mechanism. We sincerely wish our work could provide a theoretical reference for proving this novel mechanism of ESDPT experimentally. [ABSTRACT FROM AUTHOR]

[Display omitted] • Constructing Sr/Cr binuclear sites can cause significant redistribution of charge. • The adsorption sites of toluene were distributed in a trigonal prism arrangement. • The adsorption capacity of 20% Sr@MIL-101 is 60% higher than that of MIL-101. • The adsorption orientation of toluene presented disordered non-parallel adsorption. Toluene is a class of volatile organic compounds (VOCs) in the air that harm environmental quality and human health. To enhance the adsorption performance of adsorbents for toluene, based on the principle that unsaturated metal sites in MOFs can be replaced, nanoscale M@MIL-101(M represents Mg, Ca, Sr) with binuclear sites was prepared by a one-step solvothermal method. The second metal was successfully introduced into the topology of MIL-101 by partially substituting Cr sites. The results of the dynamic adsorption experiments showed that 20%Sr@MIL-101 exhibited the highest toluene adsorption capacity, which was about 60% higher than that of the undoped MIL-101. Analysis using a monolayer and multilayer model based on statistical physics theory indicated that the Sr/Cr binuclear sites could enhance the interaction strength of the adsorption system, promoting the adsorption of more layers of toluene molecules on the surface of MIL-101. Characterization and simulation together confirmed that constructing Sr/Cr binuclear sites in MIL-101 can cause significant redistribution of charge within the pores, enhancing the van der Waals interactions, π-π stacking interactions, hydrogen bonding, and Lewis acid-base interactions between the pore interior and the adsorbate molecules. Additionally, density functional theory (DFT) revealed that the adsorption sites of toluene in MIL-101 were distributed in a trigonal prism arrangement and were symmetrically aligned with a 180° rotation of the MIL-101 triangular cage. [ABSTRACT FROM AUTHOR]

Single-atom engineering offers a promising method to transform CO 2 into high-value chemicals. The local coordination structure design of the metal-support is crucial for overcoming slow reaction kinetics. In this study, Cu single atoms are immobilized on curved Bi 12 O 17 Br 2 surface to create a tip-like metal site structure named Cu tip -Bi 12 O 17 Br 2. Due to the high curvature Bi 12 O 17 Br 2 surface with tensile strain, the tip Cu creates significant electronegativity differences between adjacent Bi atomic sites, creating the vigorous polarization centers. The strong charge redistribution character of tip asymmetric Cu-Bi site favor the polarization of C O bond in nonpolar CO 2 and adjust the noncovalent to covalent interaction of reaction intermediates. Benefiting from these features, the optimized Cu tip -Bi 12 O 17 Br 2 enhance the CO production rate by a factor of 34 relative to bulk-Bi 12 O 17 Br 2 , reaching a rate of 96.99 μmol g−1 h−1. This work provides a comprehensive understanding of the structural regulation of single-atom on high curvature surface for CO 2 photoreduction. [Display omitted] • The tip enhancement effect is employed in photocatalytic CO 2 reduction. • Asymmetric Cu-Bi sites induce charge redistribution and produce strong polarization centers. • The covalent interaction between the tip-like sites and the intermediates weakens the covalent bond order of C-O. [ABSTRACT FROM AUTHOR]

Developing photocatalytic hydrogen evolution technology based on graphitic carbon nitride (g-C 3 N 4 , CN) has emerged as a potential solution for the future energy shortage in recent years. Herein, carbon (C) and fluorine (F) co-doping graphitic carbon nitride nanosheets (CFCN) were synthesized via a one-pot co-thermal method without introducing any metal element. Exceptional hydrogen production activity (3.87 mmol/h/g) was achieved by CFCN under visible light irradiation, which was 4.2-fold increase compared to the pristine CN. It could be attributed to the large specific surface area (51.59 m2/g) and efficient mass transfer facilitated by the porous sheet-like morphology of CFCN. Additionally, the modification of the band structure and internal charge redistribution were investigated via density functional theory (DFT) calculations, which confirmed there was a unidirectional and fast electron transfer channel from N through the C 4 delocalized large π bond to F. This creative research uncovered the pivotal role of F/C co-doping in enhancing photocatalytic hydrogen evolution efficacy, offering cutting-edge insights into the design of sustainable and eco-friendly photocatalysts based on metal-free CN. [Display omitted] • CFCN achieved 3.87 mmol/h/g hydrogen production, a 4.2-fold increase over pristine CN. • The porous nanosheet morphology and 51.59 m²/g surface area enhance mass transfer and activity. • Co-doping of carbon and fluorine modifies band structure, improving visible light absorption. • The DFT calculations confirm the presence of an oriented electron transfer channel. [ABSTRACT FROM AUTHOR]

Charge redistribution on surface of Ru nanoparticle can significantly affect electrocatalytic HER activity. Herein, a double atomic‐tuned RuBi SAA/Bi@OG nanostructure that features RuBi single‐atom alloy nanoparticle supported by Bi−O single‐site‐doped graphene was successfully developed by one‐step pyrolysis method. The alloyed Bi single atom and adjacent Bi−O single site in RuBi SAA/Bi@OG can synergistically manipulate electron transfer on Ru surface leading to optimum charge redistribution. Thus, the resulting RuBi SAA/Bi@OG exhibits superior alkaline HER activity. Its mass activity is up to 65000 mA mg−1 at an overpotential of 150 mV, which is 72.2 times as much as that of commercial Pt/C. DFT calculations reveal that the RuBi SAA/Bi@OG possesses the optimum charge redistribution, which is most beneficial to strengthen adsorption of water and weaken hydrogen‐adsorption free energy in HER process. This double atomic‐tuned strategy on surface charge redistribution of Ru nanoparticle opens a new way to develop highly efficient electrocatalysts. [ABSTRACT FROM AUTHOR]

[Display omitted] Electrocatalytic water splitting in an alkaline medium is recognized as the promising technology to sustainably generate clean hydrogen energy via hydrogen evolution reaction (HER), while the sluggish water dissociation and subsequent *H adsorption steps greatly retarded the reaction kinetics and efficiency of the overall hydrogen evolution process. Whilst nitrogen (N)-doped carbon-based materials are attractive candidates for promoting HER activity, the facile fabrication and gaining a deeper insight into the electrocatalytic mechanism are still challenging. Herein, inspired by the Diels-Alder reaction, we precisely tailored six-membered pyridinic N and five-membered pyrrolic N sites at the edge of the carbon substrates. Comprehensive analysis validates that the participation of pyridinic N (electron-withdrawing) and pyrrolic N (electron-releasing) will induce the charge rearrangements, and further generate local electrophilic and nucleophilic domains in adjacent carbon rings, which guarantees the occurrence of water dissociation to generate protons and the subsequent adsorption of *H intermediates through electrostatic interactions, thereby facilitating the overall reaction kinetics. To this end, the optimal NC-ZnCl 2 -25 % electrocatalysts present excellent alkaline HER activity (η 10 = 45 mV, Tafel slop of 37.7 mV dec-1) superior to commercial Pt/C. [ABSTRACT FROM AUTHOR]

Searching for functional square lattices in layered superconductor systems offers an explicit clue to modify the electron behavior and find exotic properties. The trigonal SnAs3 structural units in SnAs‐based systems are relatively conformable to distortion, which provides the possibility to achieve structurally topological transformation and higher superconducting transition temperatures. In the present work, the functional As square lattice was realized and activated in Li0.6Sn2As2 and NaSnAs through a topotactic structural transformation of trigonal SnAs3 to square SnAs4 under pressure, resulting in a record‐high Tc among all synthesized SnAs‐based compounds. Meanwhile, the conductive channel transfers from the out‐of‐plane pz orbital to the in‐plane px+py orbitals, facilitating electron hopping within the square 2D lattice and boosting the superconductivity. The reorientation of p‐orbital following a directed local structure transformation provides an effective strategy to modify layered superconducting systems. [ABSTRACT FROM AUTHOR]

Heteroatomic substitution and vacancy engineering of spinel oxides can theoretically optimize the oxygen evolution reaction (OER) through charge redistribution and d‐band center modification but still remain a great challenge in both the preparation and catalytic mechanism. Herein, we proposed a novel and efficient Ar‐plasma (P)‐assisted strategy to construct heteroatom Mo‐substituted and oxygen vacancies enriched hierarchical spinel Co3O4 porous nanoneedle arrays in situ grown on carbon cloth (denoted P‐Mo‐Co3O4@CC) to improve the OER performance. Ar‐plasma technology can efficiently generate vacancy sites at the surface of hydroxide, which induces the anchoring of Mo anion salts through electrostatic interaction, finally facilitating the substitution of Mo atoms and the formation of oxygen vacancies on the Co3O4 surface. The P‐Mo‐Co3O4@CC affords a low overpotential of only 276 mV at 10 mA cm−2 for the OER, which is 58 mV superior to that of Mo‐free Co3O4@CC and surpasses commercial RuO2 catalyst. The robust stability and satisfactory selectivity (nearly 100% Faradic efficiency) of P‐Mo‐Co3O4@CC for the OER are also demonstrated. Theoretical studies demonstrate that Mo with variable valance states can efficiently regulates the atomic ratio of Co3+/Co2+ and increases the number of oxygen vacancies, thereby inducing charge redistribution and tuning the d‐band center of Co3O4, which improve the adsorption energy of oxygen intermediates (e.g., *OOH) on P‐Mo‐Co3O4@CC during OER. Furthermore, the two‐electrode OER//HER electrolyzer equipped with P‐Mo‐Co3O4@CC as anode displays a low operation potential of 1.54 V to deliver a current density of 10 mA cm−2, and also exhibits good reversibility and anticurrent fluctuation ability under simulated real energy supply conditions, demonstrating the great potential of P‐Mo‐Co3O4@CC in water electrolysis. [ABSTRACT FROM AUTHOR]

Self-discharge, which refers to voltage depression when a power source is removed, is a crucial issue for supercapacitors (SCs). Self-discharge results in Coulombic efficiency loss and energy dissipation, and thus restricts the charge storage performance of SCs. A cost-effective and facile strategy for addressing self-discharge is newly developed in this work. It is found that self-discharge involves charge redistribution and Faradaic side reactions, which are closely associated with the pore size of activated carbon electrodes. Importantly, the pore size distribution (and thus self-discharge) can be controlled by the binder type. Specifically, a binder that maintains high macropore and mesopore fractions can effectively mitigate self-discharge. The fundamental reasons for this finding are examined. The effects of the charging rate, holding time at the full charging voltage, operation temperature, and charging cutoff voltage on the self-discharge of SCs prepared using various binders are investigated. The data reveal that binder selection also influences SC reliability in terms of the aging rate at elevated temperature and high voltage, leakage current, and gas evolution during operation. [Display omitted] • Self-discharge has long been an issue that restricts application of supercapacitors. • Electrode self-discharge involves charge redistribution and Faradaic side reactions. • A proper pore size distribution control of carbon electrode mitigates self-discharge. • A cost-effective strategy related to binder selection suppresses self-discharge. • Charging rate, temperature, and voltage all affect self-discharge rate. [ABSTRACT FROM AUTHOR]

In this work, the energy band alignments of heterostructures of 2D materials are studied, where these are crucial for various device applications. Using density functional theory (DFT), we consider heterostructures of black phosphorus (BP) with transition metal dichalcogenides [MX2, where M = molybdenum (Mo), tungsten (W), or hafnium (Hf), and X = sulfide (S) or selenide (Se)] and, specifically, the effects of charge redistribution and associated electrostatic fields on the band alignments beyond the electron affinity rule, as well as band tunability via applied layer-normal electric fields, applied strain, and layer engineering in BP/MoS2. BP is a material with high mobility and mechanical flexibility, and is also sensitive to the number of BP layers. Absent such tuning, calculations for BP combined with the more electronegative materials result in a staggered (type II) alignment for MoS2, and a broken gap (type III) alignment for HfSe2 and HfS2. Calculation for BP with less electronegative materials, WSe2, MoSe2, and WS2 materials, results in straddling (type I) alignment, with a direct gap for WSe2 and MoSe2, and an indirect gap for WS2. The amount of charge redistribution between layers and associated variations from the electron affinity rule increase going from type I to type II to type III, where the band alignment becomes significantly pinned in the latter case by the creation of mobile charge carriers. With such tuning, these band alignments can then be altered quantitatively and qualitatively. [ABSTRACT FROM AUTHOR]

Alkaline water electrolysis represents a pivotal technology for green hydrogen production yet faces critical challenges including limited current density and high energy input. Herein, a heterostructured bimetallic nitrides supported RuNi alloy (RuNi/ZrNiN x ) is developed through in situ epitaxial growth under ammonolysis, achieving exceptional bifunctional activity and durability for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in 1 m KOH electrolyte. The RuNi/ZrNiN x exhibits a HER current density of -2 A cm -2 at an overpotential of 392.8 mV, maintaining initial overpotential after 1000 h continuous electrolysis at -500 mA cm -2 . For OER, it delivers a current density of 2 A cm -2 at 1.822 V versus RHE, and sustains stable operation for 705 h at 500 mA cm -2 . Experimental and theoretical studies unveil that the charge redistribution-induced high-valence Zr centers effectively polarize H─O bonds and promote water dissociation, and the electron-deficient interface Ru sites optimize hydrogen desorption kinetics. Dynamic OH spillovers from Zr sites to the adjacent tri-coordinated Ni hollow sites in NiN x promote rapid *OH intermediate desorption and active site regeneration. Notably, the tri-coordinated Ni hollow sites in NiN x proximal to Zr atoms exhibit tailored adsorption strength for oxo-intermediates, enabling a more energetically favorable pathway for O 2 production., (© 2025 Wiley‐VCH GmbH.)

The removal of selenite (SeO 3 2- ) from water is challenging due to the risk of secondary pollutants. To address this, we developed RuO 2 -based nanocatalysts on the titanium plate (RuO 2 nanoparticles to induce charge redistribution enabled the Ru 2 nanoparticles to induce charge redistribution enabled the Ru 0.9 Sn 0.1 O x /TP catalyst to achieve ∼90% Se(IV) removal across concentrations of 0.1, 1, and 10 mM at -2 mA cm -2 over 8 h, outperforming undoped RuO 2 /TP. Furthermore, Ru 0.9 Sn 0.1 O x /TP also maintained ∼90% removal efficiency in 1 mM of Se(IV) solutions containing competitive anions (0.5 M Cl - , 0.1 M SO 4 2- , 0.01 M NO 3 - , and their mixtures), demonstrating suitability for complex wastewater treatment. Importantly, the catalysts were recyclable, with no observable contamination introduced into the solution. Density functional theory (DFT) calculations suggest that Sn doping effectively reduces the energy barrier for the reduction of Se(IV) to Se(0).