Hydrogen-Bonded Organic Cocrystal-Encapsulated Perovskite Nanocrystals as Coreactant-Free Electrochemiluminescent Luminophore for the Detection of Uranium.

Lead halide perovskite nanocrystals with excellent photophysical properties are promising electrochemiluminescence (ECL) candidates, but their poor stability greatly restricts ECL applications. Herein, hydrogen-bonded cocrystal-encapsulated CsPbBr3 perovskite nanocrystals (PeNCs@NHS-M) were synthesized by using PeNCs as nuclei for inducing the crystallization of melamine (M) and N-hydroxysuccinimide (NHS). The as-synthesized composite exhibits multiplicative ECL efficiencies (up to 24-fold that of PeNCs) without exogenous coreactants and with excellent stability in the aqueous phase. The enhanced stability can be attributed to the well-designed heterostructure of the PeNCs@NHS-M composite, which benefits from both moiety passivation and protection of the peripheral cocrystal matrix. Moreover, the heterostructure with covalent linkage facilitates charge transfer between PeNCs and NHS-M cocrystals, realizing effective ECL emission. Meanwhile, the NHS and M components act as coreactants for PeNCs, shortening the electron-transport distance and resulting in a significant increase in the ECL signal. Furthermore, by taking advantage of the specific binding effect between NHS-M and uranyl (UO22+), an ECL system with both a low detection limit (1 nM) and high selectivity for monitoring UO22+ in mining wastewater is established. The presence of UO22+ disrupted the charge-transfer effect within PeNCs@NHS-M, weakening the ECL signals. This work provides an efficient design strategy for obtaining stable and efficient ECLs from perovskite nanocrystals, offering a new perspective for the discovery and application of perovskite-based ECL systems.

σ-Hole Effect-Induced Electroluminescence of Halogen Cocrystals for Determination of Iodide in Seawater.

Developing new electrochemiluminescence (ECL) luminators with high stability, wide applicability, and strong designability is of great strategic significance to promote the ECL field to the frontier. Here, driven by the I···N bond, 1,3,5-trifluoro-2,4,6-triiodobenzene (TFTI) and 2,4,6-trimethyl-1,3,5-triazine (TMT) self-assembled into a novel halogen cocrystal (TFTI-TMT) through slow solution volatilization. Significant difference of charge density existed between the N atoms on TMT and the σ-hole of the I atoms on TFTI. Upon the induction of σ-hole effect, high-speed and spontaneous charge transferring from TMT to the σ-hole of TFTI occurred, stimulating exciting ECL signals. Besides, the σ-hole of the I atoms could capture iodine ions specifically, which blocked the original charge transfer from the N atoms to the σ-hole, causing the ECL signal of TFTI-TMT to undergo a quenching rate as high as 92.9%. Excitingly, the ECL sensing of TFTI-TMT toward I- possessed a wide linear range (10-5000 nM) and ultralow detection limit (3 nM) in a real water sample. The halogen cocrystal strategy makes σ-hole a remarkable new viewpoint of ECL luminator design and enables ECL analysis technology to contribute to addressing the environmental and health threats posed by iodide pollution.

Europium(III) Functionalized Covalent Organic Framework as Sensitive and Selective Fluorescent Switch for Detection of Uranium.

Uranium poses severe health risks due to its radioactivity and chemical toxicity if released into the environment. Therefore, there is an urgent demand to develop sensing materials in situ monitoring of uranium with high sensitivity and stability. In this work, a fluorescent Eu3+-TFPB-Bpy is synthesized by grafting Eu3+ cation onto TFPB-Bpy covalent organic framework (COF) synthesized through Schiff base condensation of monomers 1,3,5-tris(4-formylphenyl)benzene (TFPB) and 5,5'-diamino-2,2'-bipyridine (Bpy). The fluorescence of Eu3+-TFPB-Bpy is enhanced compared with that of TFPB-Bpy, which is originated from the intramolecular rotations of building blocks limited by the bipyridine units of TFPB-Bpy coordinated with Eu3+. More significantly, Eu3+-TFPB-Bpy is a highly efficient probe for sensing UO22+ in aqueous solution with the luminescence intensity efficiently amplified by complexation of UO22+ with Eu3+. The turn-on sensing capability was derived from the resonance energy transfer occurring from UO22+ to the Eu3+-TFPB-Bpy. The developed probe displayed desirable linear range from 5 nM to 5 µM with good selectivity and rapid response time (2 s) for UO22+ in mining wastewater. This strategy provides a vivid illustration for designing luminescence lanthanide COF hybrid materials with applications in environmental monitoring.

Hydrogen-Bonded Cocrystals Encapsulating CsPbBr3 Perovskite Nanocrystals with Enhancement of Charge Transport for Photocatalytic Reduction of Uranium.

At present, poor stability and carrier transfer efficiency are the main problems that limit the development of perovskite-based photoelectric technologies. In this work, hydrogen-bonded cocrystal-coated perovskite composite (PeNCs@NHS-M) is easily obtained by inducing rapid crystallization of melamine (M) and N-hydroxysuccinimide (NHS) with PeNCs as the nuclei. The outer NHS-M cocrystal passivates the undercoordinated lead atoms by forming covalent bonds, thereby greatly reducing the trap density while maintaining good structure stability for perovskite nanocrystals. Moreover, benefiting from the interfacial covalent band linkage and long-range ordered structures of cocrystals, the charge transfer efficiency is effectively enhanced and PeNCs@NHS-M displays superior photoelectric performance. Based on the excellent photoelectric performance and abundant active sites of PeNCs@NHS-M, photocatalytic reduction of uranium is realized. PeNCs@NHS-M exhibits U(VI) reduction removal capability of up to 810.1 mg g-1 in the presence of light. The strategy of cocrystals trapping perovskite nanocrystals provides a simple synthesis method for composites and opens up a new idea for simultaneously improving the stability and photovoltaic performance of perovskite.

Construction of a Bifunctional Redox-Site Conjugated Covalent-Organic Framework for Photoinduced Precision Trapping of Uranyl Ions.

The performance of covalent-organic frameworks (COFs) for the photocatalytic extraction of uranium is greatly limited by the number of adsorption sites. Herein, inspired by electronegative redox reactions, we designed a nitrogen-oxygen rich pyrazine connected COF (TQY-COF) with multiple redox sites as a platform for extracting uranium via combining superaffinity and enhanced photoinduction. The preorganized bisnitrogen-bisoxygen donor configuration on TQY-COF is entirely matched with the typical geometric coordination of hexavalent uranyl ions, which demonstrates high affinity (tetra-coordination). In addition, the presence of the carbonyl group and pyrazine ring effectively stores and controls electron flow, which efficaciously facilitates the separation of e-/h+ and enhances photocatalytic performance. The experimental results show that TQY-COF removes up to 99.8% of uranyl ions from actual uranium mine wastewater under the light conditions without a sacrificial agent, and the separation coefficient reaches 1.73 × 106 mL g-1 in the presence of multiple metal ions, which realizes the precise separation in the complex environment. Importantly, DFT calculations further elucidate the coordination mechanism of uranium and demonstrate the necessity of the presence of N/O atoms in the photocatalytic adsorption of uranium.

Structural Isomerism of Covalent Organic Frameworks Causing Different Electrochemiluminescence Effects and Its Application for the Detection of Arsenic.

The structural isomerism of the covalent organic framework (COF) has a significant effect on the electrochemiluminescence (ECL) performance. Herein, we report a pair of isomeric COFs, (TFPB-BD(OMe)2-H and TAPB-BD(OMe)2-H), based on the different directions of imine linkages and further conversion of the imine to the quinoline structure. The obtained two isomeric COFs with the same composition and similar structures exhibit dramatic differences in the photoelectrochemical and ECL fields. Indeed, TFPB-BD(OMe)2-H demonstrates robust ECL emission superior to that of TAPB-BD(OMe)2-H. The difference in ECL performance is due to the stronger polar interaction of TFPB-BD(OMe)2-H than that of TAPB-BD(OMe)2-H. The polarity is derived from the uneven charge distribution within the framework and enhances the electron interactions. In addition, the ordered conjugate skeleton provides high-speed charge transport channels for carrier transport. Therefore, the TFPB-BD(OMe)2-H presents a smaller band gap energy and stronger polarization interaction, which are more favorable to charge migration to achieve stronger ECL signals. Furthermore, we describe a convenient ECL sensor for detecting toxic As(V) with an outstanding detection property and ultralow detection limit. This work provides a guiding principle for the design and development of ECL organic luminophores.

DNAzyme-Derived Aptamer Reversely Regulates the Two Types of Enzymatic Activities of Covalent-Organic Frameworks for the Colorimetric Analysis of Uranium.

Nanozymes are nanomaterials with enzyme-mimetic activity. It is known that DNA can interact with various nanozymes in different ways, enhancing or inhibiting the activity of nanozymes, which can be used to develop various biosensors. In this work, we synthesized a photosensitive covalent-organic framework (Tph-BT) as a nanozyme, and its oxidase and peroxidase activities could be reversely regulated by surface modification of single-stranded DNA (ssDNA) for the colorimetric detection of UO22+. Tph-BT exhibits excellent oxidase activity and weak peroxidase activity, and it is surprising to find that the UO22+-specific DNA aptamer can significantly inhibit the oxidase activity while greatly enhancing the peroxidase activity. The present UO22+ interacts with the DNA aptamer to form secondary structures and detaches from the surface of Tph-BT, thereby restoring the enzymatic activity of Tph-BT. Based on the reversed regulation effects of the DNA aptamer on the two types of enzymatic activities of Tph-BT, a novel "off-on" and "on-off" sensing platform can be constructed for the colorimetric analysis of UO22+. This research demonstrates that ssDNA can effectively regulate the different types of enzymatic activities of single COFs and achieve the sensitive and selective colorimetric analysis of radionuclides by the naked eye.

Guest Molecular Assembly Strategy in Covalent Organic Frameworks for Electrochemiluminescence Sensing of Uranyl.

The application of covalent organic frameworks (COFs) in electrochemiluminescence (ECL) is promising in environmental monitoring. Developing an emerging design strategy to expand the class of COF-based ECL luminophores is highly desirable. Here, a COF-based host-guest system was constructed through guest molecular assembly to deal with nuclear contamination analysis. The efficient charge transport network was formed by inserting an electron-withdrawing guest tetracyanoquinodimethane (TCNQ) into the open space of the COF host (TP-TBDA; TP = 2,4,6-trihydroxy-1,3,5-benzenetricarbaldehyde and TBDA = 2,5-di(thiophen-2-yl)benzene-1,4-diamine) with an electron-donating property; the construction of the COF-based host-guest system (TP-TBDA@TCNQ) triggered the ECL emission of non-emitting TP-TBDA. Furthermore, the dense active sites in TP-TBDA were utilized to capture the target substance UO22+. The presence of UO22+ broke the charge-transfer effect in TP-TBDA@TCNQ, resulting in the weakening of the ECL signal, thus the established ECL system integrating the low detection limit with high selectivity monitors UO22+. This COF-based host-guest system provides a novel material platform for constructing late-model ECL luminophores and creates an opportunity for the vigorous ECL technology.

Molecular Insertion: A Master Key to Unlock Smart Photoelectric Responses of Covalent Organic Frameworks.

Covalent organic frameworks (COFs) show potentials in prominent photoelectric responses by judicious structural design. However, from the selections of monomers and condensation reactions to the synthesis procedures, the acquisition of photoelectric COFs has to meet overmuch high conditions, limiting the breakthrough and modulation in photoelectric responses. Herein, the study reports a creative "lock-key model" based on molecular insertion strategy. A COF with suitable cavity size, TP-TBDA, is used as the host to load guests. Merely through the volatilization of mixed solution, TP-TBDA and guests can be spontaneously assembled via non-covalent interactions (NCIs) to produce molecular-inserted COFs (MI-COFs). The NCIs between TP-TBDA and guests acted as a bridge to facilitate charge transfer in MI-COFs, unlocking the photoelectric responses of TP-TBDA. By exploiting the controllability of NCIs, the MI-COFs can realize the smart modulation of photoelectric responses by simply changing the guest molecule, thus avoiding the arduous selection of monomers and condensation reactions required by conventional COFs. The construction of molecular-inserted COFs circumvents complicated procedures for achieving performance improvement and modulation, providing a promising direction to construct late-model photoelectric responsive materials.

Reversed Regulation Effects of ssDNA on the Mimetic Oxidase and Peroxidase Activities of Covalent Organic Frameworks.

Nanomaterials with enzyme mimetic activity have attracted extensive attention, especially in the regulation of their catalytic activities by biomolecules or other polymers. Here, a covalent organic framework (Tph-BT COF) with excellent photocatalytic activity is constructed by Schiff base reaction, and its mimetic oxidase activity and peroxidase activity is inversely regulated via single-stranded DNA (ssDNA). Under light-emitting diode (LED) light irradiation, Tph-BT exhibited outstanding oxidase activity, which efficiently catalyzed oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to produce blue oxTMB, and ssDNA, especially those with poly-thymidine (T) sequences, can significantly inhibit its oxidase activity. On the contrary, Tph-BT showed weak peroxidase activity, and the presence of ssDNA, particularly poly-cytosine (C) sequences, can remarkably enhance the peroxidase activity. The influence of base type, base length, and other factors on the activities of two enzymes is also studied, and the results reveal that the adsorption of ssDNA on the surface of Tph-BT prevented intersystem crossing (ISC) and energy transfer processes to reduce 1 O2 generation, while the electrostatic interaction between ssDNA and TMB enhanced Tph-BT's affinity for TMB to facilitate the electron transfer from TMB to • OH. This study investigates multitype mimetic enzyme activities of nonmetallic D-A conjugated COFs and demonstrates their feasibility of regulation by ssDNA.

mUSP: a high-accuracy map of the in situ crosstalk of ubiquitylation and SUMOylation proteome predicted via the feature enhancement approach.

Reversible post-translational modification (PTM) orchestrates various biological processes by changing the properties of proteins. Since many proteins are multiply modified by PTMs, identification of PTM crosstalk site has emerged to be an intriguing topic and attracted much attention. In this study, we systematically deciphered the in situ crosstalk of ubiquitylation and SUMOylation that co-occurs on the same lysine residue. We first collected 3363 ubiquitylation-SUMOylation (UBS) crosstalk site on 1302 proteins and then investigated the prime sequence motifs, the local evolutionary degree and the distribution of structural annotations at the residue and sequence levels between the UBS crosstalk and the single modification sites. Given the properties of UBS crosstalk sites, we thus developed the mUSP classifier to predict UBS crosstalk site by integrating different types of features with two-step feature optimization by recursive feature elimination approach. By using various cross-validations, the mUSP model achieved an average area under the curve (AUC) value of 0.8416, indicating its promising accuracy and robustness. By comparison, the mUSP has significantly better performance with the improvement of 38.41 and 51.48% AUC values compared to the cross-results by the previous single predictor. The mUSP was implemented as a web server available at http://bioinfo.ncu.edu.cn/mUSP/index.html to facilitate the query of our high-accuracy UBS crosstalk results for experimental design and validation.

Rapid Charge Transfer Enabled by Noncovalent Interaction through Guest Insertion in Supercapacitors based on Covalent Organic Frameworks.

Covalent organic frameworks (COFs) have been proposed for electrochemical energy storage, although the poor conductivity resulted from covalent bonds limits their practical performance. Here, we propose to introduce noncovalent bonds in COFs through a molecular insertion strategy for improving the conductivity of the COFs as supercapacitor. The synthesized COFs (MI-COFs) establish equilibriums between covalent bonds and noncovalent bonds, which construct a continuous charge transfer channel to enhance the conductivity. The rapid charge transfer rate enables the COFs to activate the redox sites, bringing about excellent electrochemical energy storage behavior. The results show that the MI-COFs exhibit much better performance in specific capacitance and capacity retention rate than those of most COFs-based supercapacitors. Moreover, through simply altering inserted guests, the mode and strength of noncovalent bond can be adjusted to obtain different energy storage characteristics. The introduction of noncovalent bonds is an effective and flexible way to enhance and regulate the properties of COFs, providing a valuable direction for the development of novel COFs-based energy storage materials.

Tailor-Made Multiple Interpenetrated Metal-Organic Framework for Selective Detection and Adsorption of ReO4.

Rationally designed new materials for the selective detection and adsorption of 99Tc, a problematic element in nuclear waste, are important and challenging in environmental monitoring. Here, we utilize an interpenetration approach to develop a cationic fluorescent metal-organic framework (NCU-2), which was constructed by a flexible tridentate nitrogen-containing ligand and Ag+ metal ions. The NCU-2 is a scarce case of 14-fold interpenetrated with excellent chemical stability even under 0.5 M HNO3, which is helpful for the detection and removal of ReO4-/TcO4- from nuclear waste. Excitingly, the fluorescence signal of NCU-2 was obviously quenched in the presence of ReO4- (a nonradioactive surrogate of TcO4-) due to the robust interaction between ReO4- and the host for the formation of a non-fluorescent complex. Furthermore, the NCU-2 exhibits a high selectivity sensing of ReO4- in the presence of excess competitive ions. The superior response of NCU-2 toward ReO4- is ascribed to the high-fold structure and the luxuriant unsaturated Ag metal sites on the wall of 1D pore channels, which can enhance the framework positive charge and accelerate the transport of guest molecules to strengthen the interaction between them. Notably, NCU-2 successfully quantified trace levels of ReO4- in simulated Hanford waste with a broad linear range (0.2-200 µM) and a low detection limit of 66.7 nM. Moreover, NCU-2 also shows a high adsorption capacity to ReO4- (541 mg/g) and rapid sorption kinetics, making it extremely attractive for waste monitoring and emergency remediation.

Construction of Two-Dimensional Fluorescent Covalent Organic Framework Nanosheets for the Detection and Removal of Nitrophenols.

In this work, we synthesized a two-dimensional fluorescent covalent-organic framework (TFPB-TTA COF) nanosheet by selecting and designing reactive monomers to realize the dual-functional processing of nitrophenols. The staggered benzene ring, triazine structure, and imine bond (C═N) of the TFPB-TTA COF can capture free nitrophenols through hydrogen bonding and conjugation interaction, and then, the photoinduced electron transfer and fluorescence resonance energy transfer (FRET) between the TFPB-TTA COF and nitrophenols affects the fluorescence emission of the TFPB-TTA COF, realizing the fluorescence sensing of nitrophenols. The large Ksv values and the low detection limit suggest that the TFPB-TTA COF can serve as sensitive and selective fluorescence sensors for nitrophenol detection in an aqueous system. At the same time, the strong interaction combined with the porous network structure of the TFPB-TTA COF facilitates the efficient adsorption and removal of nitrophenols. Especially for 2,4,6-trinitrophenol, the maximum adsorption capacity can reach 1045.53 mg/g with good recyclability and high structural stability of the TFPB-TTA COF. This work proposed a simple synthetic method for the construction of a fluorescent COF platform for the sensitive determination and efficient adsorption of nitrophenols.

3D Ionic Olefin-Linked Conjugated Microporous Polymers for Selective Detection and Removal of TcO4-/ReO4- from Wastewater.

Technetium (99Tc) is a highly toxic radioactive nuclear wastewater contaminant. Real-time detection of 99Tc is very difficult due to its difficult-to-complex nature. Herein, a novel three-dimensional ionic olefin-linked conjugated microporous polymer (TFPM-EP-Br) is constructed using tetrakis(4-aldehyde phenyl)methane (TFPM) as the central monomer. The unique cationic cavity and highly hydrophobic framework enable TFPM-EP-Br to act as a fluorescent sensor for TcO4-. The fluorophores of TFPM-EP-Br can be quenched due to electron transfer from TFPM-EP-Br to TcO4- and the formation of strongly nonfluorescent complexes. Meanwhile, the regular pore channels are beneficial for the fast mass transfer of TcO4-, resulting in an ultrafast response time (less than 2 s) with an ultralow detection limit (33.3 nM). In addition, the ultrahigh specific surface area enables TFPM-EP-Br to combine the ability to synergistically detect and remove radioactive 99Tc. From this perspective, the novel conjugated microporous polymer has made a breakthrough in the detection and extraction of radioactive contaminants.

Covalent Organic Frameworks as Advanced Uranyl Electrochemiluminescence Monitoring Platforms.

Electrochemiluminescence (ECL), as an advanced sensing process, can selectively control the generation of excited states by changing the potential. However, most of the existing ECL systems rely on poisonous coreactants to provide radicals for luminescence; although the ECL efficiency was improved, the athematic coreactants will cause unpredictable interference to the accurate analysis of trace targets. Herein, we realized the ECL of nonemitting molecules by performing intramolecular electron transfer in the olefin-linked covalent organic frameworks (COFs), with a high efficiency of 63.7%. Employing internal dissolved oxygen as the coreactant, it is well suitable for the analysis of various complex samples in the environment. Taking nuclear contamination analysis as the goal orientation, we further illustrated a design of a "turn-on" uranyl ion monitoring system integrating fast response, low detection limit, and high selectivity, showing that new ECL-COFs are promising to facilitate environment-related sensing analysis and structure-feature correlation mechanism exploration.

Low Band Gap Benzoxazole-Linked Covalent Organic Frameworks for Photo-Enhanced Targeted Uranium Recovery.

The inherent features of covalent organic frameworks (COFs) make them highly attractive for uranium recovery applications. A key aspect yet to be explored is how to improve the selectivity and efficiency of COFs for recovering uranium from seawater. To achieve this goal, a series of robust and hydrophilic benzoxazole-based COFs is developed (denoted as Tp-DBD, Bd-DBD, and Hb-DBD) as efficient adsorbents for photo-enhanced targeted uranium recovery. Benefiting from the hydroxyl groups and the formation of benzoxazole rings, the hydrophilic Tp-DBD shows outstanding stability and chemical reduction properties. Meanwhile, the synergistic effect of the hydroxyl groups and the benzoxazole rings in the π-conjugated frameworks significantly decrease the optical band gap, and improve the affinity and capacity to uranium recovery. In seawater, the adsorption capacity of uranium is 19.2× that of vanadium, a main interfering metal in uranium extraction.

Facile Construction of Covalent Organic Framework Nanozyme for Colorimetric Detection of Uranium.

2D covalent organic frameworks (2D COFs) have been recognized as a novel class of photoactive materials owing to their extended π-electron conjugation and high chemical stabilities. Herein, a new covalent organic framework (Tph-BDP) is facilely synthesized by using a porphyrin derivative and an organic dye BODIPY derivative (5,5-difluoro-2,8-diformyl-1,3,7,9-tetramethyl-10-phenyl-5H-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabori-nin-4-ium-5-uide) as monomers for the first time, and their unique photosensitive properties endow them excellent simulated oxidase activity under 635 nm laser irradiation that can catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB). Further findings demonstrate that the presence of uranium (UO22+ ) can coordinate with imines of the oxidation products of TMB, thus modulating the charge transfer process of the colored products accompanied with intensive aggregation and remarkable color fading. This research provides a preparation strategy for COFs with excellent photocatalytic properties and nanozyme activity, and broadens the applications of the simple colorimetric methods for sensitive and selective radionuclide detection.

Nanoceria-Templated Metal Organic Frameworks with Oxidase-Mimicking Activity Boosted by Hexavalent Chromium.

The high toxicity and mobility of hexavalent chromium (Cr(VI)) allow it to easily spread and bioaccumulate, and its detection is a major part of environmental protection. In this work, an innovative method is developed for preparation of cerium oxide nanorod-templated metal-organic frameworks (CeO2NRs-MOF). The in situ growth of MOF on the surface of CeO2 nanorods (CeO2NRs) enhances its oxidase-like activity. In the presence of a trace amount of Cr(VI), CeO2NRs-MOF can significantly accelerate the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) due to Cr(VI)-boosted oxidation, resulting in a blue colored oxidation product. It can detect Cr(VI) over a range of 0.03-5 µM with high selectivity. Moreover, this method can be applied to the detection of Cr(VI) in different water environment samples with satisfactory recoveries, demonstrating the potential application of CeO2NRs-MOF for the direct monitoring of Cr(VI) in environmental water systems. Thus, this work provides a facile host-templated MOF preparation method, which could possibly be extended to other fields.

Amorphous/Crystalline Hetero-Phase TiO2 -Coated α-Fe2 O3 Core-Shell Nanospindles: A High-Performance Artificial Nitrogen Fixation Electrocatalyst.

Electrochemical nitrogen fixation techniques have emerged as a promisingly sustainable approach to face the challenge associated with nitrogen activation of ammonia synthesis by the Haber-Bosch process under ambient conditions. Herein, the performance of electrocatalytic nitrogen reduction for the production of α-Fe2 O3 nanospindles coated with mesoporous TiO2 with different crystallinity [denoted as α-Fe2 O3 @mTiO2 -X (X=300, 400, and 500 °C)] were investigated. The as-prepared α-Fe2 O3 @mTiO2 -400 composite exhibits a large NH3 yield (27.2 µg h-1 mgcat. -1 ) at -0. 5 V vs. the reversible hydrogen electrode and a high Faradaic efficiency (13.3 %) in 0.1 m Na2 SO4 , with excellent electrochemical durability. This work presents a novel avenue for the rational design of efficient unique hetero-phase nanocatalysts toward sustainable electrocatalytic N2 fixation.