Organic electrosynthesis offers a sustainable platform for redox transformation under mild conditions, where radical intermediates play pivotal roles. However, direct structural characterization of these transient species remains challenging, particularly under operando conditions, hindering mechanistic understanding and reaction design. Herein, via digital light processing (DLP) 3D-print technology, we have designed the electrolytic flat cell for operando electron paramagnetic resonance (EPR) tests to track radical intermediates in real time. This architecture ensures precise electrode positioning within tailored channels, which could increase the electrodes' overlap area to reduce the resistance and improve the signal-to-noise ratio, alongside good mechanical robustness with low fabrication costs. Through time-resolved EPR technology, the formation order of amino and phenolic radicals has been demonstrated, confirming the radical addition of phenothiazine N-centered radical to p-methoxyphenol in C-N cross-coupling; Two resonance structures of benzenesulfonamide, the aryl pi radical and N-centered radical, could be distinguished by EPR analysis, which helps to clarify the chemo- and regioselectivity in (3 + 2) annulation; Solvent-mediated radical rearrangement inspired the design of a selective C-O cross-coupling between diphenylamine and phenol, demonstrating the importance of confirming intermediate structure for reaction design. Given the universality of this in-situ EPR platform, we believe it provides robust support for monitoring active intermediates in electrochemical reactions and elucidating reaction mechanisms.

A solvent-polarity-directed strategy has been developed to synthesize multicolor silane-functionalized carbon dots from citric acid and an organosilane through a solvothermal reaction. These synthesized silane-functionalized carbon dots can then be integrated with a violet-emitting chip to fabricate a full-spectrum white light-emitting diode, showing a color rendering index of 92.

Interfacial solar desalination is often hindered by complex fabrication, high cost, and the "low-cost vs high-performance" trade-off. However, beyond material cost, a fundamental challenge lies in achieving the coordinated regulation of heat localization, water transport, and vapor diffusion within simple and scalable systems. Herein, we report a grid-structured paper-based solar evaporator using traditional Chinese ink, an eco-friendly, low-cost photothermal material composed of nanoscale carbon black and gelatin binder. Commercial filter paper is folded into a three-dimensional (3D) grid architecture. Only the outer surface of grid is coated with ink prepared by grinding traditional ink sticks. This architecture spatially decouples photothermal conversion from internal water transport pathways by confining heat generation to the external surface, while preserving rapid capillary-driven water supply within the uncoated paper-based network. The grid structure further promotes lateral vapor diffusion and establishes spatially distributed evaporation interfaces, thereby enabling coordinated regulation of heat and mass transfer processes. This enables synergistic solar-ambient energy harvesting: solar energy contributes similar to 84.6%, ambient energy similar to 15.4%, and total heat loss similar to 9.7%. Under 1 sun illumination, the evaporator achieves a high evaporation rate of 3.12 kg m(-2) h(-1), with a salt-rejection rate >99.9% (meets WHO standards). It maintains stable operation over 14 consecutive cycles in 3.5 wt % NaCl solution. Notably, the material cost per device is <1 US cent, with no specialized equipment or hazardous chemicals required. This work proposes a design strategy based on "functional partitioning and three-dimensional structural regulation," within which material distribution, water transport, and thermal management are integrally optimized on a simple paper-based platform. This framework provides a scalable and mechanism-driven pathway for achieving high-performance interfacial solar desalination.

The competitive adsorption between H* and OH* on single active sites is a long-standing bottleneck limiting alkaline hydrogen evolution reaction (HER) kinetics. Herein, we integrate "multi-element electronic regulation" with "dual-site functional partitioning" in a PtRuFeCoNi high-entropy alloy (HEA) electrocatalyst, which is synthesized via high-entropy engineering strategy. Driven by electronegativity differences among Pt, Ru, Fe, Co, and Ni, spontaneous electron transfer precisely modulates their d-band centers of Pt and Ru. This electronic regulation results in that Pt sites activate H2O and adsorb OH*, while Ru sites optimize H* adsorption free energy to -0.18 eV for selective H* stabilization. Operando EPR directly captures ·H's "generation-stabilization-conversion" dynamics, filling the characterization gap. Complemented by in situ Raman and FTIR, the dual-site mechanism is validated. PtRuFeCoNi/catalyst exhibits an ultra-low overpotential of 5.2 mV at 10 mA cm-2, a Tafel slope of 45.6 mV dec-1, and 150 h stability in 1 M KOH. For overall water splitting, it achieves 10 mA cm-2 at 1.41 V, outperforming Pt/C||RuO2. This work establishes a new paradigm for resolving intermediate adsorption competition in multi-electron transfer reactions.

In single-atom catalysts, the coordination microenvironment surrounding transition-metal centers is widely recognized as a key factor shaping their electronic structures and geometries, thereby governing catalytic behaviors. However, the synergetic catalysis between metal center and ligating atoms remains underexplored in single-atom catalysis. Herein, we construct the Pd(II)-N4 sites on carbon nitride to achieve photocatalytic semi-hydrogenation of alkynes. Under light irradiation, the Pd-N sites could transform to H-Pd···N-H moieties. The Pd-H center enhances alkyne insertion while the adjacent N-H group facilitates intramolecular proton transfer. This metal-ligand cooperativity of H-Pd···N-H sites, together with the steric-hindrance imposed by carbon nitride scaffold, lowers the energy barrier for Z-alkene formation and ensures exclusive stereoselectivity. Simultaneously, the H-Pd···N-H sites exhibit stronger adsorption toward alkynes than alkenes, effectively suppressing over-hydrogenation to alkanes. Across all evaluated substrates, Z-alkenes are the only isomers detected, excluding E-isomer and alkane. Notably, in a 5:95 mixture of diphenylacetylene and Z-stilbene, this method selectively converts only the alkyne to the Z-isomer without over-hydrogenation, highlighting its potential for product purification. Metal–ligand synergistic catalysis remains underexplored in single-atom systems. Here, inspired by homogeneous pincer complexes, the authors construct Pd(II)–N₄ sites on carbon nitride, enabling highly selective photocatalytic semi-hydrogenation of alkynes.

The integration of carbon dots (CDs) with graphitic carbon nitride (g-C3N4) has emerged as a promising approach to enhance photocatalytic hydrogen (H2) evolution. Despite significant progress, critical challenges remain in achieving broad visible-light absorption and suppressing charge recombination. In this work, we developed a series of photocatalysts through in situ embedding of red-emissive CDs (R-CDs) into g-C3N4 (RCN) with precisely controlled loading amounts. Systematic characterization revealed that the R-CDs incorporation simultaneously addresses two fundamental limitations: (1) extending the light absorption edge to 800 nm, and (2) acting as an electron acceptor, facilitating charge separation. The optimized RCN composite demonstrates exceptional H2 evolution activity (1.87 mmolg-1h-1, wavelength (lambda) >= 420 nm), representing a 3.3-fold enhancement over pristine g-C3N4. Remarkably, the apparent quantum efficiency (AQE) reaches 9.1% at 420 nm, while maintaining measurable activity beyond 475 nm, where unmodified g-C3N4 shows negligible response. This study provides fundamental insights into band structure engineering and charge carrier management through rational design of CDs-modified semiconductor heterostructures.

The outer-sphere single-electron transfer (SET) is the main pathway for activating substrates during semiconductor photocatalysis, which is limited by energy band structure and excited-state lifetime. Under light irradiation, the inner-sphere ligand-to-metal charge transfer (LMCT) from substrate to metal species can break through the above limitations and be complementary to the SET process. However, this LMCT activation mode has rarely been involved in heterogeneous semiconductor photocatalysis. Herein, we build Fe - N_{2} single atom sites on carbon nitride (Fe + (- N_{2}) / C * N) and achieve the photocatalytic decarboxylative Giese reaction via radical-radical cross-coupling (up to 99% yields). This Fe + (- N_{2}) / C * N photocatalyst has both LMCT and SET activity, which could activate carboxylic acids and electron-deficient alkenes simultaneously. The carboxylic acid could coordinate with Fe sites and convelt into alkyl radical via photo-induced LMCT decarboxylation pathway. Meanwhile, the electron-deficient olefins could be activated to radical anion through single-electron reduction by electrons in the conduction band of carbon nitride. Combining the LMCT and SET strategy opens a new avenue for the design of semiconductor catalysts, expanding the scope of photocatalytic redox reactions.

Membrane distillation (MD) is a promising technology for desalinating saline wastewater, but its efficiency is constrained by membrane fouling and wetting. To elucidate the role of nanocatalytic Fenton oxidation in enhancing MD performance for hydraulic fracturing produced water (HFPW) treatment, this study employs hydrolyzed aluminum and iron nanoparticles as active catalysts, with commercial Cu2O included as a benchmark. The three oxidative pretreatment methods increased the normalized flux from 0.46 to over 0.85. Under optimal conditions, Fe-based Fenton achieved removal rates of 67.86% (UV254), 41.96% (fluorescent organics), and 83.19% (hydrophobic organics), outperforming the other two systems. The extended Derjaguin-Landau-Verwey-Overbeek theory showed that the energy barrier was nearly doubled compared to the HFPW, and both exceed 40 kT. Density functional theory calculations show Fe-based catalysts strongly adsorb and activate H2O2, enabling energetically favorable •OH formation, whereas Al-based catalysts exhibit non-spontaneous H2O2 adsorption and instead act primarily through pollutant adsorption and flocculation. The superiority of Fe-based Fenton MD systems was further confirmed during long-term operation. Overall, this study has efficiently improved MD performance through the use of simply prepared nanocatalyst and provided the corresponding mechanism, offering a promising solution to the membrane fouling and wetting problems during long-term MD operation.

Alloying Pt with Pd is a pivotal strategy to regulate Pt’s electronic state and enhance its activity toward the oxygen reduction reaction (ORR). However, the weak interaction between traditional carbon supports and PtPd clusters severely limits precise modulation of their electronic structure and intermediate adsorption, restricting electrocatalytic performance. Herein, we propose a gradient support engineering strategy to address this challenge. We designed PtPd cluster-based catalysts anchored on pristine C, CN/C, and Ga single-atom doped CN/C (Ga1-CN/C), constructing a gradient system that evolves from “weak metal-support interaction” to “strong metal-support interaction” for systematically investigating the support regulation effect on ORR performance. Specifically, CN/C support strengthens metal-support interactions (MSI) via Pt/Pd-N coordination to tune electronic distribution. Notably, Ga1-CN/C further boosts MSI through Ga-PtPd p-d hybridization, which finely modulates PtPd’s d-band center to optimize its electronic state and ORR intermediate adsorption energy. Meanwhile, Ga’s empty p-orbitals effectively promote O2 adsorption. Consequently, PtPd/Ga1-CN/C exhibits a half-wave potential of 0.895V (vs. RHE) and a mass activity of 0.44Amg-1(Pt+Pd) at 0.9V (6.47 times that of commercial Pt/C). Assembled into a Zn-air battery (ZAB), it delivers an open-circuit voltage of 1.54V and superior cycling stability for over 168h. In-situ Raman and DFT calculations confirm enhanced MSI promotes O2 activation and reduces the *OOH cleavage barrier. This work provides a feasible paradigm for designing high-performance electrocatalysts via support-engineered MSI.

p-d orbital hybridization offers a powerful strategy to optimize oxygen adsorption energies and accelerate the oxygen reduction reaction (ORR) in zinc-air batteries (ZABs). Here, we introduce Group IIIA elements (Al, Ga, In) into PdPtMo metallenes to systematically tune p-d orbital interactions. Among them, Ga exhibits the smallest atomic radius mismatch and optimal orbital energy alignment, and the enhanced p-d orbital hybridization in PdPtMoGa metallenes promotes electron transfer. The PdPtMoGa metallene/C catalyst achieves an exceptionally high mass activity of 6.07 A mg-1Pt at 0.9 V vs. RHE and a half-wave potential of 0.94 V, surpassing commercial Pt/C. Density functional theory calculations, X-ray absorption spectroscopy, in-situ Fourier-transform infrared spectroscopy, and other characterizations reveal that the strong p-d orbital hybridization induced by Ga coordination with Pd in PdPtMoGa metallenes lowers the d-band center and weakens the adsorption of oxygen intermediates. Remarkably, the catalyst retains stability over 30,000 cycles. When deployed in ZABs, PdPtMoGa metallene/C achieves a peak power density of 207.2 mW cm-2 and stable operation exceeding 180 h. Overall, this study presents a rational design strategy for high-activity and durable Pd-based electrocatalysts and elucidates the specific roles of Group IIIA elements in modulating p-d orbital hybridization. (c) 2026, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Mineral scaling and scaling-induced wetting are major challenges for the widespread application of membrane distillation (MD) in saline wastewater treatment. For the first time, an in-line modified activated alumina (AA) granular filtration coupled with MD process was proposed to achieve effective control of gypsum scaling. Firstly, the AA modified by NaOH impregnation with tuned pore structure and surface characteristics were supplied as the filter media. The optimized MD performance was obtained using in-line filtration with modified AA (MAA) with 20 g/L NaOH and the ratio of AA and NaOH solution of 1:3 for the duration of 24 h. Compared with severe scaling without granular filter, the optimized performance with a final normalized flux higher than 0.7 and a permeate conductivity less than 5 mu S/cm at 70 % water recovery was observed. The MAA with rich pore, scale- like structures and high Na loading showed a superior ability in capturing gypsum scaling due to the enhanced heterogeneous scaling and the retention of scaling. In-line granular filtration-MD was also effective in mitigating gypsum scaling and scaling-induced wetting in saline solutions (e.g., 7-12 g/L NaCl). Our findings provide guidance for surface design of granular filter media and scaling control in membrane desalination technology.

Dual-atom catalysts (DACs) are promising for various catalytic reactions. However, synthesis challenges have hindered their development. Herein, we propose a universal approach using photoinduced ligand exchange (PILE) to create DACs with high proportions of dual-atom pairs, fixed interatomic distances, and tunable metal ratios and types. By cocrystallizing two metal acetylacetonates on graphitic carbon nitride (CN) nanosheets, the metal types and ratios in DACs can be precisely controlled. Remarkably, over 90% of dual-atom pairs follow the metal atom distances of 2.4 and 7.3 & Aring;. During the photocatalytic H2 production, the heteronuclear DAC (Pt1Pd2/CN) delivers a performance of similar to 15.9 mmolg-1h-1 under AM1.5 light irradiation due to the electron synergistic effect, which overperforms not only the single-atom catalysts (Pt/CN and Pd/CN) but also the homonuclear DACs (PtPt/CN and PdPd/CN). X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge structure (XANES), and density functional theory (DFT) calculations reveal that Pt draws electrons from Pd, modulating its charge state, lowering the d-orbital center and approaching the more proper H adsorption free energy, thereby enhancing H2 production. As a pioneering strategy, PILE offers a straightforward and powerful route to synthesize both homonuclear and heteronuclear DACs, holding immense promise for revolutionizing a broad spectrum of catalytic applications.

The membrane electrochemical reactor (MER), integrating oxidation, softening, and acidification within a single system, has demonstrated significant potential in mitigating membrane fouling during leachate treatment. However, the specific contributions of oxidation, softening, and acidification in the MER, along with their synergistic effects on membrane fouling control, remain inadequately understood. In this study, leachate was regulated with different MER-related strategies before membrane distillation treatment, and Differential logtransformed absorbance spectra, electrochemical impedance spectroscopy, Derjaguin-Landau-VerweyOverbeek theory were employed to investigate the membrane fouling mechanism. The results indicates that oxidation effectively removed the organic matter, thereby mitigating the hydrophobic interactions between the membrane and foulant. However, it also promoted the deprotonation of carboxyl groups in organic matter, such as polysaccharides and proteins, enhancing the complexation of multivalent cations. Acidification and softening reduced organic-inorganic complexation fouling by inhibiting carboxylate deprotonation and reducing Ca2+ and Mg2+ concentrations, respectively. These processes counteracted the adverse effects of oxidation while further mitigating organic fouling and inorganic scaling. Additionally, the synergistic effects of oxidation, softening, and acidification effectively prevented foulants from entering membrane pores and enhanced wetting resistance. Overall, this study demonstrated the potential of combining oxidation, softening, and acidification while elucidating their mechanisms in mitigating membrane fouling.

High-entropy metallenes (HEMs), combining high-entropy alloys and ultrathin nanosheets, exhibit lattice strain, geometric effects, and electronic modulation, enhancing oxygen reduction reaction (ORR) activity. We propose a strategy to manipulate the interfacial electric field and electronic density of states in HEMs by adjusting atomic radius and electronegativity differences. Integrating smaller atomic radius elements (Fe/Co/Ni) with larger ones (Pt/Pd/Mo) increases nanosheet curvature, altering the local electric field. Lowelectronegativity Fe/Co/Ni/Mo elements lower the d-band center of Pd, and Pt further decreases it, reducing oxygen intermediate adsorption energy. PtPdFeCoNiMo HEMs, with sub-nanometer thickness, high curvature, microstrain, and optimized electronic structure, achieve ORR mass activity of 1.40 A$mgPt-1 at 0.9 V (vs. reversible hydrogen electrode [RHE]) in 0.1 M KOH, 21 times higher than Pt/C. They retain excellent performance after 20,000 cycles, with reduced energy barriers for the rate-determining ORR step.

Mineral scaling and scaling-induced wetting are critical issues in membrane distillation (MD) during treatment of saline wastewaters. Gypsum scaling and scaling-induced wetting in MD were successfully regulated by heterogeneous crystallization with in-line granular filtration in this study. Stable water recovery increased from 32.5 % to more than 52.5 % in one-cycle operation, depending on filter media properties. Because a large mass of crystals were retained or/and adsorbed in the granular filter, the scaling mass on membrane surface was reduced by 41.2 %, 23.1 %, 54.7 % and 78.1 % by filter charged with activated carbon, sand, fiber and activated alumina, respectively. When activated carbon, sand, fiber and activated alumina were used, the final MD fluxes were 1.58, 1.04, 1.96 and 3.43 times that without filter, and permeate conductivity decreased by 43.0 %, 46.8 %, 83.2 % and 81.3 %, respectively. The multi-cycle tests showed that heterogeneous crystallization gradually occurred in the granular filter, thereby promoting seeding-induced crystallization that reduced gypsum scaling and scaling-induced wetting in MD. Excellent anti-scaling and anti-wetting performance of in-line granular filtration was also confirmed for synthetic and real industrial wastewater. The results of this study provide guidance for mineral scaling control in MD to allow resource utilization for saline wastewater.

In recent years,with the development of carbon dots in terms of synthesis routes,reaction mechanisms,and optical properties,a large amount of work has focused on carbon dots that emit long wavelengths such as infrared or near-infrared.Long wavelength refers to the red or near-infrared spectral region whose emission range is 600-1 800 nm.Compared with short-wavelength carbon dots,they have the characteristics of deep tissue penetration,less autofluorescence,long fluorescence lifetime and less light damage,and can be further applied in the fields of biomedical treatment,optoelectronics and optical device preparation.Therefore,in-depth exploration of the design and synthesis of long-wavelength emitting carbon dots is of great significance for their development and wide applica-tion.This article reviews the research progress of long-wavelength carbon dots in recent years,and introduces how to prepare long-wavelength carbon dots from two aspects:carbon source selection and control of optical properties.For example,choose some aliphatic compounds containing more amino groups and aromatic compounds with conjugated structures.And its optical properties can be controlled through changing the effective conjugation length,surface modification,and heteroatom doping.Finally,the latest research and future challenges of long-wavelength carbon dots in some fields such as biomedicine,LED optics,encryption and anti-counterfeiting are introduced.

In synergistic catalysis, multiple catalysts or active sites work together to produce ‘the whole is greater than the sum of its parts’ effect. However, the trilemma of flexibility-stability-cost lies ahead of the multiunit heterogeneous catalyst. As complexity increases, the catalytic efficiency tends to be restricted. Here, we report a general method to tailor modular metallaphotoredox catalysts. The dyes and molecular catalysts could flexibly connect with inexpensive carbon nitride via stable covalent bonds, like LEGO® games. Tunable visible-light absorption, high electron-hole separation efficiency and steerable construction of catalytic active sites have been realized simultaneously, meanwhile the electron transfer mechanism has been clarified via operando techniques. By precisely regulating the coordination field of single-atom sites, four different metallaphotoredox-enabled C-C cross-couplings could be compatible with good cyclic stability (up to 150 hours) and anti-interference ability.

Understanding the valency and structural variations of metal centers during reactions is important for mechanistic studies of single-atom catalysis, which could be beneficial for optimizing reactions and designing new protocols. Herein, we precisely developed a single-atom Cu(I)-N4 site catalyst via a photoinduced ligand exchange (PILE) strategy. The low-valent and electron-rich copper species could catalyze hydrophosphinylation via a novel single-electron oxidative addition (OA) pathway under light irradiation, which could considerably decrease the energy barrier compared with the well-known hydrogen atom transfer (HAT) and single electron transfer (SET) processes. The Cu(I)-Cu(II)-Cu(I) catalytic cycle, via single-electron oxidative addition and photoreduction, has been proven by multiple in situ or operando techniques. This catalytic system demonstrates high efficiency and requires room temperature conditions and no additives, which improves the turnover frequency (TOF) to 1507 h-1. In particular, this unique mechanism has broken through the substrate limitation and shows a broad scope for different electronic effects of alkenes and alkynes.

The production of freshwater from seawater via solar energy is currently a hot research topic. Nonetheless, the accumulation of salt on the evaporator's surface during the evaporation process significantly impedes both the rate and efficiency of water evaporation. Consequently, there is an urgent necessity to ingeniously design the evaporator structure in order to mitigate salt precipitation, marking a critical challenge in device engineering. This study presents a pioneering 3D micro-lattice structural hydrogel evaporator, meticulously crafted utilizing state-of-the-art 3D printing technology, tailored expressly for the solar desalination of highly saline waters. Its hierarchical porous architecture amplifies water transportation and light absorption capabilities, concurrently enabling swift relocation of salt ions away from the evaporative surface, thereby thwarting salt buildup. Remarkably, the hydrogel preserves its structural robustness amidst high-concentration brine environments and fosters proficient heat concentration at the air-water interface, yielding freshwater output rates surpassing 3.5 kg m- 2 h-1 even under stringent conditions of 20 wt% NaCl solutions, exhibiting unparalleled performance and durability across multiple operational cycles. This research paves the way for sustainable and efficient solar desalination systems, showcasing the potential of micro-lattice structures in hydrogels for enhanced salt rejection and improved water recovery rates in challenging environments.