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An asymmetric aza-BODIPY analogue bearing quinoxaline moiety was synthesized via a titanium tetrachloride-mediated Schiff-base-forming reaction of 6,7-dimethyl-1,4-dihydroquinoxaline-2,3-dione and benzo[d]thiazol-2-amine. This novel aza-BODIPY analogue forms a complementary hydrogen-bonded dimer due to the quinoxaline moiety in the crystal structure. It also shows intense absorption and fluorescence, with fluorescence quantum yields close to unity. The electrochemical measurements and the DFT calculations revealed the presence of the low-lying HOMO, which benefits their potential applications as an electron-transporting material.

Siliceous microplankton is an effective proxy for connecting modern and past marine environments; however, radiolarians have been understudied in Prydz Bay, Eastern Antarctica. This study investigated the changes in the siliceous microbiota fluxes and radiolarian assemblages captured in a 1-year time-series sediment trap (February 2014 to February 2015, ~490 m water depth) in the polynya of Prydz Bay. The results exhibited the strong seasonality in the radiolarian assemblages and the fluxes of radiolarians, diatoms, silicoflagellates and sponge spicules, with low numbers in winter and high numbers in summer. Seasonal variations in the sea ice and plankton community were critical in these patterns. The total radiolarian flux (TRF) displayed three peaks with higher flux than the annual average TRF over the year, all of which occurred in summer. These TRF peaks were mainly driven by seasonal fluctuations of sea ice, primary productivity, grazing pressure caused by phytophagous zooplankton and resuspension of small radiolarians in the surface sediments induced by modified Circumpolar Deep Water (mCDW) intrusion onto the shelf. There were also two notable low-TRF stages, mainly related to full sea-ice coverage and high grazing pressure. Two dominant assemblages were recognized by means of Q-factor analysis. Dominant assemblage one was composed of three small-sized taxa, Antarctissa sp., Phormacantha hystrix and Plectacantha oikiskos, which could be used as a proxy for primary productivity in the Marginal Ice Zone (MIZ) in Prydz Bay. Dominant assemblage two was composed of Antarctissa strelkovi and Antarctissa denticulata, with A. strelkovi dominating. The high flux and high relative abundance of A. strelkovi marked the extension of Ice Shelf Water (ISW) to the shelf area in Prydz Bay. These findings will provide new insights and reliable proxies for modern and paleoceanographic research in the Southern Ocean.

Examining iron (Fe) speciation in marine sediments is critical to understand Fe and carbon biogeochemical cycling in polar regions. In this study, we investigated the speciation of Fe in sediments from Prydz Bay and the adjacent Southern Ocean, and examined the factors controlling Fe speciation and its relationship with total organic carbon (TOC). Our results reveal that unreactive silicate Fe (FeU) is the dominant pool of total Fe (FeT), followed by poorly reactive sheet silicate Fe (FePRS), reducible crystalline Fe oxides (Feox2), easily reducible amorphous/poorly crystalline Fe oxides (Feox1), and magnetite (Femag), with carbonate-associated ferrous Fe (Fecarb) being the smallest pool. The highly reactive Fe (FeHR)/FeT ratios (0.13 ± 0.06) in our study area are among the lowest end-member globally, primarily due to weak bedrock weathering and slow glacier melting. The Feox1/FeT ratios are similar to those in continental shelf and marginal seas containing highly weathered materials, while the Feox2/FeT ratios are significantly lower. This result implicates that low temperature inhibits the aging of iceberg melting-sourced Feox1 potentially, and accordingly the regulation of weathering on the FeHR/FeT ratio is mainly reflected in Feox2/FeT ratio. There are no significant correlations between TOC and FeHR, Fecarb, Feox1 or Feox2 in the research region. Four distinct patterns of TOC/FeHR ratio can be discerned by summarizing the global data set: (a) high TOC/FeHR ratios (> 2.5) are likely the result of high marine primary productivity and low chemically weathered source materials; (b) low TOC/FeHR ratios (< 0.6) are caused by high rates of FeHR inputs and OC remineralization; (c) mid-range TOC/FeHR ratios (0.6 – 2.5) typical of most river particulates and marginal sea sediments indicate the same FeHR and OC sources and/or interactions between each other; (d) both low TOC and FeHR content is the result of low marine primary productivity and weak chemical weathering. Our findings provide new insights into the relationship between FeHR and TOC in polar sediments.

Nucleoside analogs play a crucial role in the production of high-value antitumor and antimicrobial drugs. Currently, nucleoside analogs are mainly obtained through nucleic acid degradation, chemical synthesis, and biotransformation. However, these methods face several challenges, such as low concentration of the main product, the presence of complex matrices, and the generation of numerous by-products that significantly limit the development of new drugs and their pharmacological studies. Therefore, this work aims to summarize the universal separation methods of nucleoside analogs, including crystallization, high-performance liquid chromatography (HPLC), column chromatography, solvent extraction, and adsorption. The review also explores the application of molecular imprinting techniques (MITs) in enhancing the identification of the separation process. It compares existing studies reported on adsorbents of molecularly imprinted polymers (MIPs) for the separation of nucleoside analogs. The development of new methods for selective separation and purification of nucleosides is vital to improving the efficiency and quality of nucleoside production. It enables us to obtain nucleoside products that are essential for the development of antitumor and antiviral drugs. Additionally, these methods possess immense potential in the prevention and control of serious diseases, offering significant economic, social, and scientific benefits to the fields of environment, biomedical research, and clinical therapeutics.

In this work, a sialic acid (SA)-imprinted thermo-responsive hydrogel layer was prepared for selective capture and release of cancer cells. The SA-imprinting process was performed at 37 °C using thermo-responsive functional monomer, thus generating switchable SA-recognition sites with potent SA binding at 37 °C and weak binding at a lower temperature (e.g., 25 °C). Since SA is often overexpressed at the glycan terminals of cell membrane proteins or lipids, the SA-imprinted hydrogel layer could be used for selective cancer cell recognition. Our results confirmed that the hydrogel layer could efficiently capture cancer cells from not only the culture medium but also the real blood samples. In addition, the captured cells could be non-invasively released by lowing the temperature. Considering the non-invasive processing mode, considerable capture efficiency, good cell selectivity, as well as the more stable and durable SA-imprinted sites compared to natural antibodies or receptors, this thermo-responsive hydrogel layer could be used as a promising and general platform for cell-based cancer diagnosis.

Oil pollution caused by a large number of industrial activities and oil spill accidents has posed serious harm to the environment and human health. However, some challenges remain with the existing separation materials, such as poor stability and fouling resistance. Herein, a TiO2/SiO2 fiber membrane (TSFM) was prepared by a one-step hydrothermal method for oil-water separation in acid, alkali, and salt environments. The TiO2 nanoparticles were successfully grown on the fiber surface, endowing the membrane with superhydrophilicity/underwater superoleophobicity. The as-prepared TSFM exhibits high separation efficiency (above 98%) and separation fluxes (3016.38–3263.45 L·m−2·h−1) for various oil-water mixtures. Importantly, the membrane shows good corrosion resistance in acid, alkaline, and salt solutions and still maintains underwater superoleophobicity and high separation performance. The TSFM displays good performance after repeated separation, demonstrating its excellent antifouling ability. Importantly, the pollutants on the membrane surface can be effectively degraded under light radiation to restore its underwater superoleophobicity, showing the unique self-cleaning ability of the membrane. In view of its good self-cleaning ability and environmental stability, the membrane can be used for wastewater treatment and oil spill recovery and has a broad application prospect in water treatment in complex environments.

Reliable records of Southern Ocean seawater palaeotemperatures are important because this region plays a significant role in regulating global climate change. Biomarkers such as GDGT-based indices have been effectively used to reconstruct seawater temperatures. We analysed the composition and distribution of iGDGTs, OH-GDGTs and brGDGTs and calculated GDGT-based temperature indices in surface sediments from Prydz Bay, East Antarctica. Our results showed that iGDGTs, OH-GDGTs and brGDGTs are all produced in situ, with iGDGTs and OH-GDGTs mostly synthesized by Thaumarchaeota. Concentrations of iGDGTs, OH-GDGTs and brGDGTs showed similar spatial distributions and decreased from the continental shelf towards the deep ocean. The highest concentrations were in the inner bay, which is attributed to a combination of (1) bathymetry that reduces water exchange, (2) the Prydz Bay Gyre stabilizing the upper water column and (3) sea ice that releases archaea and bacteria. Among the temperature indices based on iGDGTs, OH-GDGTs and combinations therein, those based on OH-GDGTs showed the strongest correlation with seawater temperature. Some OH-GDGT-based indices (e.g., OH-0/OHs, OH-1/OHs, OH-2/OHs and RI-OH′) exhibited a stronger correlation with annual subsurface ocean temperature (100–200 m), which may be related to archaeal habitats and production mechanisms. Our study suggests that RI-OH′ and OH-0/OHs could be used as indicators of annual subsurface ocean temperature in Antarctic marginal seas.

Hollow mesoporous silica nanoparticles have been widely applied as a carrier material in the molecular imprinting process because of their excellent properties, with high specific surface area and well-defined active centers. However, these kinds of materials face the inevitable problem that they have low mass transfer efficiency and cannot be conveniently recycled. In order to solve this problem, this work has developed a composite hydrogel microsphere (MMHSG) encapsulated with hollow mesoporous imprinted nanoparticles for the selective extraction of 2’-deoxyadenosine (dA). Subsequently, the hollow mesoporous imprinted polymers using dA as template molecule and synthesized 5-(2-carbomethoxyvinyl)-2′-deoxyuridine (AcrU) as functional monomer were encapsulated in hydrogel. MMHSG displayed good performance in specifically recognizing and quickly separating dA, whereas no imprinting effect was observed among 2′-deoxyguanosine (dG), deoxycytidine (dC), or 5′-monophosphate disodium salt (AMP). Moreover, the adsorption of dA by MMHSG followed chemisorption and could reach adsorption equilibrium within 60 min; the saturation adsorption capacity was 20.22 μmol·g−1. The introduction of AcrU could improve selectivity through base complementary pairing to greatly increase the imprinting factor to 3.79. Therefore, this was a successful attempt to combine a hydrogel with hollow mesoporous silica nanoparticles and molecularly imprinted material.

In this work, an olive oil-filled composite capsule (C–O/W) adsorbent was prepared for the adsorption of 3,4,5-trichlorophenol (3,4,5-TCP) by the emulsion templating method. Using methylene diisocyanate (HDI) and 1,6-hexanediamine (HMDA) as functional monomers, olive oil was encapsulated in a shell layer composed of graphene oxide and a polymer by interfacial imine polymerization. The contaminant target was efficiently removed by the hydrophobic interaction between olive oil and chlorophenols. The removal of 3,4,5-TCP was remarkable, with an encapsulation rate of 85%. The unique microcapsule structure further enhanced the kinetic performance, which reached 92% of the maximum value within 40 min. The adsorption of different chlorophenols was investigated using 2-chlorophenol (2-CP), 2,6-dichlorophenol (2,6-DCP), and 3,4,5-TCP. The adsorption of 3,4,5-TCP by the C-O/W microcapsules was found to be much higher than that of other chlorophenols. When analyzing a real sample, the content of 3,4,5-TCP was significantly reduced after adsorption by the C-O/W microcapsules, demonstrating that the C-O/W microcapsules were also capable of removing 3,4,5-TCP from a complex environment. This simple and inexpensive preparation strategy provides a new method for the synthesis of functionalized C-O/W microcapsule adsorbents and an effective adsorbent of 3,4,5-TCP.

Uranium is an indispensable part of the nuclear industry that benefits us, but its consequent pollution of water bodies also makes a far-reaching impact on human society. The rapid, efficient and convenient extraction of uranium from water is to be a top priority. Thanks to the super hydrophilic and fast adsorption rate of microgel, it has been the ideal adsorbent in water; however, it was too difficult to recover the microgel after adsorption, which limited its practical applications. Here, we developed a uranyl-ion affine and recyclable microgel container that has not only the rapid swelling rate of microgel particles but also allows the detection of the adsorption saturation process by the naked eye.

Simulation of self-recovery and diversity of natural photonic crystal (PC) structures remain great challenges for artificial PC materials. Motivated by the dynamic characteristics of PC nanostructures, here, we present a new strategy for the design of hydrogel-based artificial PC materials with reversible interactions in the periodic nanostructures. The dynamic PC hydrogels, derived from self-assembled microgel colloidal crystals, were tactfully constructed by reversible crosslinking of adjacent microgels in the ordered structure via phenylboronate covalent chemistry. As proof of concept, three types of dynamic colloidal PC hydrogels with different structural colors were prepared. All the hydrogels showed perfect self-healing ability against physical damage. Moreover, dynamic crosslinking within the microgel crystals enabled shear-thinning injection of the PC hydrogels through a syringe (indicating injectability or printability), followed by rapid recovery of the structural colors. In short, in addition to the great significance in biomimicry of self-healing function of natural PC materials, our work provides a facile strategy for the construction of diversified artificial PC materials for different applications such as chem-/biosensing, counterfeit prevention, optical display, and energy conversion.

To improve the output and quality of agricultural products, pesticides are globally utilized as an efficient tool to protect crops from insects. However, given that most pesticides used are difficult to decompose, they inevitably remain in agricultural products and are further enriched into food chains and ecosystems, posing great threats to human health and the environment. Thus, developing efficient methods and tools to monitor pesticide residues and related biomarkers (acetylcholinesterase and butylcholinesterase) became quite significant. With the advantages of excellent stability, tailorable catalytic performance, low cost, and easy mass production, nanomaterials with enzyme-like properties (nanozymes) are extensively utilized in fields ranging from biomedicine to environmental remediation. Especially, with the catalytic nature to offer amplified signals for highly sensitive detection, nanozymes were finding potential applications in the sensing of various analytes, including pesticides and their biomarkers. To highlight the progress in this field, here the sensing principles of pesticides and cholinesterases based on nanozyme catalysis are definitively summarized, and emerging detection methods and technologies with the participation of nanozymes are critically discussed. Importantly, typical examples are introduced to reveal the promising use of nanozymes. Also, some challenges in the field and future trends are proposed, with the hope of inspiring more efforts to advance nanozyme-involved sensors for pesticides and cholinesterases.

The submicrosized imprinted polypropylene microfiltration membrane (SIPM) for salicylic acid (SA) was prepared by water-in-oil emulsion polymerization method and two-dimensional imprinting method based on polypropylene microfiltration membrane with salicylic acid as template molecule, 4-vinyl pyridine as functional monomer, Span 80 as emulsifier, toluene as the oil phase, ethyleneglycol dimethacrylate as cross-linking agent, and 2,2′-azobis (2-methylpropionitrile) as initiator. The structure, morphology, and surface wettability of SIPM were characterized by Raman spectra, contact angle, and scanning electron microscopy. Flux test shows that the submicrosized imprinted spheres on the membrane is beneficial for increasing the membrane flux. Static adsorption experiment indicates that SIPM has a selective rebinding for salicylic acid. Moreover, the adsorption amount of salicylic acid over SIPM increased with properly increasing the amount of imprinted spheres on the SIPM. Permeation experiment shows that transport mechanism for permeation of the salicylic acid and acetylsalicylic acid toward SIPM is accordance with the facilitated mechanism.

Highly effective magnetic molecularly imprinted polymer (MMIP) beads for adsorption of 2,4,6-trichlorophenol (2,4,6-TCP) were synthesized by suspension polymerization. The effect of various parameters such as bed depths (0.6, 1.1 and 1.7 cm), flow rate (1, 2 and 3 ml minute −1 ), influent 2,4,6-TCP concentrations (50, 100 and 200 mg l −1 ), influent solution pH (4, 6 and 8) and temperature (288, 298 and 308 K) was investigated. The breakthrough time increased with the increase of the bed depth, but decreased with an increase of the initial concentration, flow rate and temperature. The Adams–Bohart and Thomas models were applied to the adsorption process under experimental conditions to predict the breakthrough curves for process design. The Thomas model was in good agreement with the experimental data. Compared with magnetic non-imprinted polymers, MMIPs exhibited an excellent selectivity towards 2,4,6-TCP.

Poly(styrene–divinylbenzene)/Fe 3 O 4 (Fe 3 O 4 @St–DVB) magnetic porous polymer microspheres based on suspension polymerization were prepared for adsorption of 2, 4-dichlorophenol (2, 4-DCP) and 2, 6-dichlorophenol (2, 6-DCP) from aqueous solution. The as-prepared product was characterized by Fourier transform infrared spectroscopy, Raman, X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, differential thermal analysis and elemental analysis. The results showed that the composite material has both porous and magnetic characteristics, which aid in faster separation and increase in adsorption capacity. The adsorption performance of the Fe 3 O 4 @(St–DVB) magnetic porous microspheres was manifested by batch mode adsorption experiments with respect to pH, initial concentration, contact time and temperature. The adsorbent was found to be sensitive to changes in pH, and the adsorption capacity of 2, 4-DCP is higher than that of 2, 6-DCP. The kinetics experimental data fitted well with the pseudo-second-order model, as three steps belonged to the pseudo-second-order adsorption process. The adsorption isotherms were also described by the Langmuir and Freundlich isotherm models, respectively. It was found that the Langmuir isotherm model fitted the equilibrium data superior to the Freundlich model. Thermodynamic parameters were calculated by the Gibbs free energy function, confirming that adsorption process was spontaneous and endothermic. In addition, the reusability performance of the Fe 3 O 4 @(St–DVB) magnetic porous microspheres was demonstrated by four repeated cycles.

Herein, we explain an effective method for the synthesis of halloysite/CoFe 2 O 4 magnetic composites (magnetic halloysite nanotubes or MHNTs) and their use as as adsorbents to effectively remove tetracycline hydrochloride (TC–HCl) from aqueous solutions. The synthesized composites were characterized by the following methods: Fourier transform infrared, X-ray diffraction, transmission electron microscopy, vibrating sample magnetometry and atomic absorption spectrometry. Our study results indicated that MHNTs have strong magnetic (Ms = 34.02 emu/g) and low leakage properties. The adsorption capacities of MHNTs were investigated by performing a series of experiments with different pH, temperatures, initial concentrations and reaction time. The Langmuir isotherm model fitted to equilibrium data better than the Freundlich model. The kinetic properties of the composites were well-described by applying the pseudo-second-order equation. Even after carrying out two repeated experimental cycles, the reusability of the synthesized composites did not obviously degenerate.

The freeze-dried biomass of Paecilomyces lilacinus was employed as a biosorbent for the removal of silver ions from aqueous solution. The effects of factors such as the solution pH, the initial Ag(I) ion concentration, contact time and temperature were examined. Maximum Ag(I) adsorption was obtained at pH 3.0. The pseudo-first-order, pseudo-second-order and intra-particle diffusion kinetic models were fitted to the experimental data when it was found that such data were best fitted by the pseudo-second-order kinetic model. The equilibrium experimental data were well fitted by the Langmuir model (R 2 > 0.995) and the maximum biosorption capacity at 298 K was 101.0 mmol/g. Thermodynamic parameters such as the Gibbs' free energy, ΔG 0 , the standard enthalpy, ΔH 0 , and the standard entropy, ΔS 0 , were evaluated. The results indicated that the biosorption of Ag(I) ions onto P. lilacinus biomass was spontaneous and endothermic in nature. The FT-IR analysis results indicated that amine, carboxylic and hydroxyl groups were involved in the biosorption process.

Raw palygorskite was modified by the addition of selected surfactants, viz. hexadecyltrimethylammonium bromide (CTAB), cetylpyridinium bromide (CPB) and octadecyldimethylbenzyl ammonium chloride (ODBAC). These modified clays were used as sorbents for the adsorptive removal of 2,6-dichlorophenol (2,6-DCP) from aqueous solution. Characterization of the sorbents was achieved by Fourier-transform infrared (FT-IR) analysis, nitrogen adsorption/desorption measurements and particle-size analysis. The adsorptive performance of the modified palygorskites towards the removal of 2,6-DCP from aqueous solution was studied by batch methods. In addition, the influence of contact time, pH and temperature on the adsorption process was investigated in detail. The equilibrium data for the three modified sorbents were well fitted by the Langmuir model. It was found that the monolayer adsorption capacity increased with increasing contact time and solution temperature, respectively. Application of the pseudo-first-order and pseudo-second-order kinetic models to the kinetic data showed that the pseudo-second-order kinetic model provided an excellent fit (R 2 > 0.99). In addition, the film diffusion, pore diffusion and intra-particle diffusion models were also used to investigate the adsorption mechanism. Intra-particle diffusional analysis indicated that 2,6-DCP molecules diffused rapidly during the initial adsorption stage, followed by a slower stage and finally the establishment of an equilibrium condition. Thermodynamic studies showed that the adsorption of 2,6-DCP onto the three sorbents examined occurred spontaneously and that the process was endothermic in nature. The results indicate that the surfactant-modified palygorskite exhibited a significant potential as a sorbent material for the removal of phenolic compounds from aqueous solution.

Molecular imprinting has been conducted on the surface of TiO 2 particles to enable the recognition of dibenzothiophene (DBT) molecules. This was achieved via the use of a novel surface molecular-imprinting technique. The adsorption behaviour of the dibenzothiophene-imprinted material (D-MIP/TiO 2 ) was evaluated using batch adsorption experiments to determine the kinetic, isotherm and thermodynamic parameters. The experimental results showed that the adsorption process followed pseudo-second-order kinetics and that the experimental data were well fitted by the Freundlich adsorption equation. This indicated that adsorption involved a multilayer process. Values of the Gibbs' free energy (ΔG 0 ) ranged from −7.11 kJ/mol to −9.36 kJ/mol over the temperature interval 298–318 K, indicating that the adsorption was endothermic in nature. In addition, D-MIP exhibited selective recognition of DBT relative to other similar compounds such as benzothiophene (BT), 4-methyldibenzothiphene (4-MDBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT). In the corresponding selectivity test, D-MIP/TiO 2 showed a greater adsorption capacity towards DBT than BT, 4-MDBT and 4,6-DMDBT. The large imprinting factor (ca. 2.5) exhibited by D-MIP/TiO 2 for DBT could be explained in terms of a covalent assembly mechanism.

Novel surface strontium(II) ion-imprinted adsorbent particles have been prepared via the copolymerization of chitosan as the monomer, γ-(2,3-epoxypropoxy)propyltrimethoxysilane (KH-560) as the cross-linking agent and 2,2′-azobisisobutyronitrile (AIBN) as the initiator in the presence of SrCl 2 • 6H 2 O. The prepared imprinted adsorbent was used for the selective solid-phase extraction (SPE) of trace Sr(II) ions in a practical sample prior to its determination by inductively coupled plasma–atomic emission spectrometry (ICP–AES). The results suggest that the adsorption kinetic data accorded better with the pseudo-second-order model, while the adsorption equilibrium data gave a good fit to the Langmuir isotherm equation, yielding a maximum adsorption capacity of 27.58 mg/g and a Langmuir adsorption equilibrium coefficient of 0.0363 ℓ/mg at 298 K. The relative selectivity coefficient values of Sr(II) ion-imprinted particles were several times greater than those for the non-imprinted matrix. The new Sr(II) ion-imprinted micro-beads were successfully applied for the separation of Sr(II) ions from river and clay samples. The detection limit (3σ) for Sr(II) ions as determined by flame atomic absorption spectrometry (FAAS) was 0.21 ng/mℓ. The relative standard deviation (RSD) for the determination of Sr(II) ions was 6–9% over the concentration range 0.03–0.3 mg/ℓ.

Electrocatalytic nitrogen reduction is a challenging process that requires achieving high ammonia yield rate and reasonable faradaic efficiency. To address this issue, this study developed a catalyst by in situ anchoring interfacial intergrown ultrafine MoO2 nanograins on N-doped carbon fibers. By optimizing the thermal treatment conditions, an abundant number of grain boundaries were generated between MoO2 nanograins, which led to an increased fraction of oxygen vacancies. This, in turn, improved the transfer of electrons, resulting in the creation of highly active reactive sites and efficient nitrogen trapping. The resulting optimal catalyst, MoO2/C700, outperformed commercial MoO2 and state-of-the-art N2 reduction catalysts, with NH3 yield and Faradic efficiency of 173.7 µg h-1 mg-1 cat and 27.6%, respectively, under - 0.7 V vs. RHE in 1 M KOH electrolyte. In situ X-ray photoelectron spectroscopy characterization and density functional theory calculation validated the electronic structure effect and advantage of N2 adsorption over oxygen vacancy, revealing the dominant interplay of N2 and oxygen vacancy and generating electronic transfer between nitrogen and Mo(IV). The study also unveiled the origin of improved activity by correlating with the interfacial effect, demonstrating the big potential for practical N2 reduction applications as the obtained optimal catalyst exhibited appreciable catalytic stability during 60 h of continuous electrolysis. This work demonstrates the feasibility of enhancing electrocatalytic nitrogen reduction by engineering grain boundaries to promote oxygen vacancies, offering a promising avenue for efficient and sustainable ammonia production. [ABSTRACT FROM AUTHOR]