Zeolitic imidazolate framework derived Fe catalyst electrocatalytic-driven atomic hydrogen for efficient reduction of nitrate to N2.

Excessive discharge of nitrogen-containing chemical products into the natural water environment leads to the serious environmental problem of nitrate-nitrogen pollution, threatening the ecological balance and human health. In this study, we propose an efficient denitrification electrochemical method utilizing iron-doped zeolite imidazolium framework derived defective nitrogen-doped carbon (d-FeNC) catalysts. The d-FeNC catalyst exhibited 97 % nitrate removal efficiency and 94 % total nitrogen (TN) removal, and the reaction rate constant was increased from 0.73 h-1 of the Fe-undoped electrocatalyst (d-NC) to 1.11 h-1. The successful synthesis of d-FeNC with carbon defect sites and encapsulated Fe was confirmed by in-depth characterization. In situ electron paramagnetic resonance (EPR) analysis in conjunction with cyclic voltammetry (CV) tests confirmed the carbon substrates with defect enhanced the trapping of atomic hydrogen (H*) on the catalyst surface. Density functional theory (DFT) calculations clarified the doping of Fe facilitated the adsorption of nitrate, resulting in contact of H* with nitrate on the catalyst surface. In the synergy of the defective state organic framework and metal Fe, H* and nitrate realized a collision process. The electrochemical denitrification system achieved an excellent nitrate removal capacity of 7587 mgN·g-1cat in high-concentration nitrate solution and showed excellent stability under various conditions. Overall, this study underscores the potential of defective iron-doped carbon catalysts for efficient electrocatalytic denitrification, providing a promising approach for sustainable wastewater treatment.

Synthesis of composite materials combining magnetic metal-organic frameworks and conjugated organic frameworks for selective extraction of carbendazim and thiabendazole residues from Chinese herbal medicine samples.

A magnetic metal-organic framework MIL-68(Al) and a covalent organic framework were used as magnetic solid-phase extraction (MSPE) adsorbents in combination with high-performance liquid chromatography ultraviolet detection (HPLC-UV) to detect carbendazim (CBZ) and thiabendazole (TBZ). The main parameters affecting the extraction in the MSPE process were studied and optimized. Fe3O4@MIL-68(Al) coated with 1,3,5-tris(4-aminophenyl)benzene and terephthaldehyde (Fe3O4@MIL-68(Al)@TAPB-PDA-COF) was analyzed and verified. The material was proven to be suitable for adsorbing CBZ and TBZ. Various adsorption models were used to study its adsorption mechanism. The adsorption results were in good agreement with the pseudo-second-order kinetic model and Langmuir isotherm model. The maximum adsorption capacities of Fe3O4@MIL-68(Al)@TAPB-PDA-COF over CBZ and TBZ were 54.24 and 67.87 mg g-1, respectively, and the equilibrium adsorption time was 200 min. Fe3O4@MIL-68(Al)@TAPB-PDA-COF with excellent recyclability showed higher adsorption capacity and selectivity. A method based on Fe3O4@MIL-68(Al)@TAPB-PDA-COF combined with HPLC-UV was established under the optimal extraction conditions and used to separate and detect trace imidazole drugs in Chinese herbal samples, achieving a low limit of detection (0.65-1.30 µg L-1) with excellent linear correlation (r > 0.999). The recovery rate and relative standard deviation were 86.05-99.78 % and 0.15-4.90 %, respectively. Therefore, the Fe3O4@MIL-68@TAPB-PDA-COF can be regarded as an effective adsorbent for the pretreatment of CBZ and TBZ drugs in Chinese herbal samples.

Phosphate Adsorption on Cerium/Terephthalic Acid Metal-Organic Frameworks (Ce-MOF) Driven by Effective Electrostatic Attraction and Ligand Exchange in a Wide pH Range.

Eutrophication has posed a threat to aquatic ecosystems, so it's urgent to remove excessive phosphate from water. In this study, we developed an adsorbent material, cerium/terephthalic-acid metal-organic-frameworks (Ce-MOF), to remove phosphate from different water systems. The optimal Ce-MOF presented a maximum phosphate adsorption capacity of 377.2 mg/g, approximately 3.7 times higher than that of the commercial phosphate adsorbent (Phoslock: 101.6 mg/g). Experimental and computational analysis suggested that pH dominated the adsorption process. The main forces driving the adsorption process changed from the synergistic effect of electrostatic attraction and ligand exchange at lower pH to only ligand exchange at the increased pH values. Hence, the Ce-MOF is applicable for phosphate adsorption in a wide pH range. Impressively, the adsorbent remained an excellent phosphate adsorption performance in the real water containing various interfering ions and organic matters, indicating the potential of Ce-MOF for the practical use to solve the water eutrophication issue.

Thin-wall hollow porous cystic-like graphitic carbon nitride with awakened n→π* electronic transitions and exceptional structural features for superior photocatalytic degradation of sulfamethoxazole.

Effective photoexcitation and carrier migration are the essential aspects to strengthen semiconductor-engaged redox reaction. Herein, a three-dimensional thin-wall hollow porous cystic-like g-C3N4 (HPCN) with curved layer edge was successfully fabricated via a non-template thermal-condensation strategy. The construction of unique distorted structure can evoke the hard-to-activate n→π* electronic transition to some extent, broadening the absorption spectrum to 800 nm. And benefiting from the multiple reflections of incident light, the effective photoactivation can be further achieved. Moreover, the thin-wall porous framework can shorten the diffusion distance and accelerate migration of photogenerated charge, favouring interfacial redox reactions. The optimized HPCN1.0 demonstrated an excellent photocatalytic degradation of SMX under blue-LED light irradiation, which was dramatically superior to that of pristine g-C3N4 (CN, 11.4 times). Ultimately, in consideration of reactions under several influencing factors with four different water samples, we demonstrated that the HPCN photocatalyst could be utilized far more productively for the elimination of SMX under real-world aqueous conditions. This work provides a straightforward approach for the removal of SMX and has immense potential to contribute to global scale environmental remediation.

Construction of dual transfer channels in graphitic carbon nitride photocatalyst for high-efficiency environmental pollution remediation: Enhanced exciton dissociation and carrier migration.

Graphitic carbon nitride (g-C3N4) is a promising candidate for photocatalysis, but exhibits moderate activity due to strongly bound excitons and sluggish charge migration. The dissociation of excitons to free electrons and holes is considered an effective strategy to enhance photocatalytic activity. Herein, a novel boron nitride quantum dots (BNQDs) modified P-doped g-C3N4 photocatalyst (BQPN) was successfully prepared by thermal polymerization method. Photoluminescence techniques and photoelectrochemical tests demonstrated that the introduction of P atoms and BNQDs promoted the dissociation of excitons and the migration of photogenerated carriers. Specifically, theoretical calculations revealed that P substitutions were the sites of pooled electrons, while BNQDs were the excellent photogenerated hole extractors. Accordingly, compared with g-C3N4, the BQPN showed improved performance in degrading four non-steroidal anti-inflammatory drugs (NSAIDs) under visible light irradiation. This work not only establishes an in-depth understanding of excitonic regulation in g-C3N4, but also offers a promising photocatalytic technology for environmental remediation.

Construction of double-functionalized g-C3N4 heterojunction structure via optimized charge transfer for the synergistically enhanced photocatalytic degradation of sulfonamides and H2O2 production.

Herein, supporting g-C3N4 embedded with benzene-ring (BCN) on P-modified g-C3N4 (PCN) successfully synthesized the homogeneous photocatalyst BCN/PCN (PBCN) via a simple thermal polymerization reaction. Under blue-light (LED) irradiation, the optimized PBCN (0.448 min-1) demonstrated excellent photocatalytic performance, attaining over 74 times the degradation rate for sulfisoxazole (SSZ) in contrast to non-functionalized g-C3N4 (CN, 0.006 min-1). Theoretical calculations revealed that the substitution of heterocyclic rings in the g-C3N4 triazine networks with benzene-rings enabled them to serve as electron donors, while promoting photoinduced spatial charge dissociation. Further, the carrier PCN tended to serve as electron acceptors to form electron-rich corner-phosphorous sites. Reactive species experiments demonstrate that the O2˙- and h+ constituted the primary photocatalytic mechanism of SSZ degradation. The potential SSZ degradation routes were predicted based on the transformation products via mass spectrometry. Finally, the composite materials also exhibited excellent photocatalytic activity in the conversion of solar energy to chemical energy (H2O2). This study guides the rational modification of g-C3N4-based semiconductors to achieve green energy production and beneficial ecological applications.

Synchronous construction of a porous intramolecular D-A conjugated polymer via electron donors for superior photocatalytic decontamination.

The development of conjugated polymers with intramolecular donor-acceptor (D-A) units has the capacity to enhance the photocatalytic performance of carbon nitride (g-C3N4) for the removal of antibiotics from ambient ecosystems. This strategy addresses the challenge of narrowing the band gap of g-C3N4 while maintaining its high LUMO position. For this study, we introduced the above donor units into g-C3N4 to construct intramolecular D-A structures through the copolymerization of dicyandiamide with creatinine, which strategically extended light absorption into the green region and expedited photoelectron separation. The introduction of electron donor blocks kept the LUMO distributed on the melem, which maintained the high LUMO energy level of the copolymer with the potential to generate oxygen radicals. The as-prepared porous D-A conjugated polymer enhanced the photocatalytic degradation of sulfisoxazole with kinetic constants 5.6 times higher than that of g-C3N4 under blue light and 15.3 times higher under green light. Furthermore, we surveyed the degradation mechanism including the effective active species and degradation pathways. This study offers a new perspective for the synchronous construction of a porous intramolecular D-A conjugated polymer to enhance water treatment and environmental remediation capacities.

An Improved ACKF/KF Initial Alignment Method for Odometer-Aided Strapdown Inertial Navigation System.

For a land-vehicle strapdown inertial navigation system (SINS), the problem of initial alignment with large misalignment angle in-motion needs to be solved urgently. This paper proposes an improved ACKF/KF initial alignment method for SINS aided by odometer. The SINS error equation with large misalignment angle is established first in the form of an Euler angle. The odometer/gyroscope dead reckoning (DR) error equation is deduced, which makes the observation equation linear when the position is taken as the observation of the Kalman filter. Then, based on the cubature Kalman filter, the Sage-Husa adaptive filter and the characteristics of the observation equation, an improved ACKF/KF method is proposed, which can accomplish initial alignment well in the case of unknown measurement noise. Computer simulation results show that the performance of the proposed ACKF/KF algorithm is superior to EKF, CKF and AEKF method in accuracy and stability, and the vehicle test validates its advantages.

Perinatal iodine deficiency and hypothyroidism increase cell apoptosis and alter doublecortin and reelin protein expressions in rat cerebellum.

BACKGROUND AND AIMS: Adequate thyroid hormone is critical for cerebellar development. Developmental hypothyroidism induced by iodine deficiency during the perinatal period results in permanent impairments of cerebellar development with an unclear mechanism. In the present study we investigated effects of perinatal iodine deficiency and hypothyroidism on cerebellar cell apoptosis, doublecortin (Dcx) and reelin. Apoptosis is an essential part of neural development. Dcx and reelin are two important molecules involved in neuronal migration, structure, and development in cerebellum. METHODS: Two developmental rat models were created by administering dam rats with either iodine-deficient diet or propylthiouracil (PTU, 5 ppm or 15 ppm)-added drinking water from gestational day (GD) 6 until postnatal day (PND) 28. TUNEL assay and protein levels of Dcx and reelin in cerebella were assessed on PND14, 21 and 28. RESULTS: Apoptotic cells were increased in the iodine-deficient and PTU-treated rats. Dcx protein levels in the cerebella of iodine-deficient and PTU-treated rats were significantly downregulated on PND14. Interestingly, iodine deficiency and PTU treatment upregulated the levels of Dcx protein on PND21 and 28. Reelin expressions in iodine-deficient and PTU-treated rats were significantly decreased on PND14 and 21. On PND28, reelin expressions of three treated groups were still lower than control group, although without significant difference. CONCLUSIONS: These findings may implicate alterations in cell apoptosis and levels of Dcx and reelin in the impairments of cerebellar development induced by developmental iodine deficiency and hypothyroidism.

Developmental iodine deficiency and hypothyroidism impair neural development, upregulate caveolin-1, and downregulate synaptotagmin-1 in the rat cerebellum.

Adequate thyroid hormone is critical for cerebellar development. Developmental hypothyroidism induced by iodine deficiency during gestation and postnatal period results in permanent impairments of cerebellar development with an unclear mechanism. In the present study, we implicate cerebellar caveolin-1 and synaptotagmin-1, the two important molecules involved in neuronal development, in developmental iodine deficiency, and in developmental hypothyroidism. Two developmental rat models were created by administrating dam rats with either iodine-deficient diet or propylthiouracil (PTU, 5 or 15 ppm)-added drinking water from gestational day 6 till postnatal day (PN) 28. Nissl staining and the levels of caveolin-1 and synaptotagmin-1 in cerebella were assessed on PN28 and PN42. The results show that the numbers of Purkinje cells were reduced in the iodine-deficient and PTU-treated rats. The upregulation of caveolin-1 and the downregulation of synaptotagmin-1 were observed in both iodine-deficient and PTU-treated rats. These findings may implicate decreases in the number of Purkinje cells and the alterations in the levels of caveolin-1 and synaptotagmin-1 in the impairments of cerebellar development induced by developmental iodine deficiency and hypothyroidism.

Developmental iodine deficiency and hypothyroidism impair neural development in rat hippocampus: involvement of doublecortin and NCAM-180.

BACKGROUND: Developmental iodine deficiency results in inadequate thyroid hormone (TH), which damages the hippocampus. Here, we explored the roles of hippocampal doublecortin and neural cell adhesion molecule (NCAM)-180 in developmental iodine deficiency and hypothyroidism. METHODS: Two developmental rat models were established with either an iodine-deficient diet, or propylthiouracil (PTU)-adulterated water (5 ppm or 15 ppm) to impair thyroid function, in pregnant rats from gestational day 6 until postnatal day (PN) 28. Silver-stained neurons and protein levels of doublecortin and NCAM-180 in several hippocampal subregions were assessed on PN14, PN21, PN28, and PN42. RESULTS: The results show that nerve fibers in iodine-deficient and 15 ppm PTU-treated rats were injured on PN28 and PN42. Downregulation of doublecortin and upregulation of NCAM-180 were observed in iodine-deficient and 15 ppm PTU-treated rats from PN14 on. These alterations were irreversible by the restoration of serum TH concentrations on PN42. CONCLUSION: Developmental iodine deficiency and hypothyroidism impair the expression of doublecortin and NCAM-180, leading to nerve fiber malfunction and thus impairments in hippocampal development.