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1.
Chem Commun (Camb) ; 2024 Jul 12.
Article in English | MEDLINE | ID: mdl-38993020

ABSTRACT

The oxygen reduction reaction (ORR) via the two-electron pathway is an important method of hydrogen peroxide (H2O2) production. This study demonstrates that MnO with different oxygen vacancies possesses great 2e- ORR activity. The H2O2 selectivity increased from 10% to 93% with increasing oxygen vacancy concentration by adjusting the reaction temperature and time. Moreover, the H2O2 yield of the optimal MnO reached 544.1 mmol g-1 h-1, and it showed extraordinary stability over a long period of time (10 000 circles CV), surpassing most of the reported transition metal catalysts. This provides a new strategy for efficient and low-cost electrochemical production of H2O2.

2.
Adv Mater ; : e2407534, 2024 Jul 08.
Article in English | MEDLINE | ID: mdl-38973643

ABSTRACT

Understanding the water-involved mechanism on metal oxide surface and the dynamic interaction of water with active sites is crucial in solving water poisoning in catalytic reactions. Herein, this work solves this problem by designing the water-promoted function of metal oxides in the ethanol oxidation reaction. In situ multimodal spectroscopies unveil that the competitive adsorption of water-dissociated *OH species with O2 at Sn active sites results in water poisoning and the sluggish proton transfer in CoO-SnO2 imparts water-resistant effect. Carbon material as electron donor and proton transport channel optimizes the Co active sites and expedites the reverse hydrogen spillover from CoO to SnO2. The water-promoted function arises from spillover protons facilitating O2 activation on the SnO2 surface, leading to crucial *OOH intermediate formation for catalyzing C-H and C-C cleavage. Consequently, the tailored CoO-C-SnO2 showcases a remarkable 60-fold enhancement in ethanol oxidation reaction compared to bare SnO2 under high-humidity conditions.

3.
Heliyon ; 10(12): e32963, 2024 Jun 30.
Article in English | MEDLINE | ID: mdl-38994042

ABSTRACT

The sustainable advancement of agriculture stands as the fundamental cornerstone of sustainable human progress. This study introduces a data-centric methodological framework founded upon the holistic delineation of measurement, feature assessment, and pathway enhancement for agricultural sustainability. Initially, the research articulates a comprehensive evaluative schema incorporating sub-dimensions encompassing agricultural production, agricultural economics, the agricultural resource environment, and rural society, grounded in sustainable development theory. Subsequently, it devises a methodological apparatus for assessing and enhancing sustainable development capabilities, employing entropy evaluation methods and exploratory spatial data analysis techniques. Employing North Anhui as a case study, the viability of this approach is substantiated. The empirical inquiry conducted within this article operationalizes comprehensive evaluation and explores pathways for optimizing agricultural sustainability, focusing on the period spanning 2011 to 2020 in Northern Anhui. The findings affirm the feasibility and efficacy of the data-driven approach. Recommendations derived from the empirical exploration of agricultural sustainability pathways at the local level offer valuable insights for governmental authorities and policymakers. This research endeavor could be extrapolated to other geographical locales worldwide, fostering innovative strides in the sustainable development of regional agriculture.

4.
Cell Rep ; 43(7): 114410, 2024 Jun 25.
Article in English | MEDLINE | ID: mdl-38923457

ABSTRACT

Polymyxins are often the only effective antibiotics against the "Critical" pathogen Acinetobacter baumannii. Worryingly, highly polymyxin-resistant A. baumannii displaying dependence on polymyxins has emerged in the clinic, leading to diagnosis and treatment failures. Here, we report that arginine metabolism is essential for polymyxin-dependent A. baumannii. Specifically, the arginine degradation pathway was significantly altered in polymyxin-dependent strains compared to wild-type strains, with critical metabolites (e.g., L-arginine and L-glutamate) severely depleted and expression of the astABCDE operon significantly increased. Supplementation of arginine increased bacterial metabolic activity and suppressed polymyxin dependence. Deletion of astA, the first gene in the arginine degradation pathway, decreased phosphatidylglycerol and increased phosphatidylethanolamine levels in the outer membrane, thereby reducing the interaction with polymyxins. This study elucidates the molecular mechanism by which arginine metabolism impacts polymyxin dependence in A. baumannii, underscoring its critical role in improving diagnosis and treatment of life-threatening infections caused by "undetectable" polymyxin-dependent A. baumannii.

5.
Sci Rep ; 14(1): 14079, 2024 06 18.
Article in English | MEDLINE | ID: mdl-38890341

ABSTRACT

While cryogenic electron microscopy (cryo-EM) is fruitfully used for harvesting high-resolution structures of sizable macromolecules, its application to small or flexible proteins composed of small domains like immunoglobulin (IgG) remain challenging. Here, we applied single particle cryo-EM to Rituximab, a therapeutic IgG mediating anti-tumor toxicity, to explore its solution conformations. We found Rituximab molecules exhibited aggregates in cryo-EM specimens contrary to its solution behavior, and utilized a non-ionic detergent to successfully disperse them as isolated particles amenable to single particle analysis. As the detergent adversely reduced the protein-to-solvent contrast, we employed phase plate contrast to mitigate the impaired protein visibility. Assisted by phase plate imaging, we obtained a canonical three-arm IgG structure with other structures displaying variable arm densities co-existing in solution, affirming high flexibility of arm-connecting linkers. Furthermore, we showed phase plate imaging enables reliable structure determination of Fab to sub-nanometer resolution from ab initio, yielding a characteristic two-lobe structure that could be unambiguously docked with crystal structure. Our findings revealed conformation diversity of IgG and demonstrated phase plate was viable for cryo-EM analysis of small proteins without symmetry. This work helps extend cryo-EM boundaries, providing a valuable imaging and structural analysis framework for macromolecules with similar challenging features.


Subject(s)
Cryoelectron Microscopy , Immunoglobulin Fab Fragments , Immunoglobulin G , Protein Conformation , Cryoelectron Microscopy/methods , Immunoglobulin Fab Fragments/chemistry , Immunoglobulin Fab Fragments/ultrastructure , Immunoglobulin G/chemistry , Rituximab/chemistry , Humans , Models, Molecular
6.
Chemistry ; : e202401674, 2024 Jun 05.
Article in English | MEDLINE | ID: mdl-38839567

ABSTRACT

Nitrile-aminothiol conjugation (NATC) stands out as a promising biocompatible ligation technique due to its high chemo-selectivity. Herein we investigated the reactivity and substrate scope of NAT conjugation chemistry, thus developing a novel pH dependent orthogonal NATC as a valuable tool for chemical biology. The study of reaction kinetics elucidated that the combination of heteroaromatic nitrile and aminothiol groups led to the formation of an optimal bioorthogonal pairing, which is pH dependent. This pairing system was effectively utilized for sequential and dual conjugation. Subsequently, these rapid (≈1 h) and high yield (>90%) conjugation strategies were successfully applied to a broad range of complex biomolecules, including oligonucleotides, chelates, small molecules and peptides. The effectiveness of this conjugation chemistry was demonstrated by synthesizing a fluorescently labelled antimicrobial peptide-oligonucleotide complex as a dual conjugate to imaging in live cells. This first-of-its-kind sequential NATC approach unveils unprecedented opportunities in modern chemical biology, showcasing exceptional adaptability in rapidly creating structurally complex bioconjugates. Furthermore, the results highlight its potential for versatile applications across fundamental and translational biomedical research.

7.
J Am Chem Soc ; 146(23): 15977-15985, 2024 Jun 12.
Article in English | MEDLINE | ID: mdl-38713009

ABSTRACT

Unveiling innovative mechanisms to design new highly efficient fluorescent materials and, thereby, fabricate high-performance organic light-emitting diodes (OLEDs) is a concerted endeavor in both academic and industrial circles. Polycyclic aromatic hydrocarbons (PAHs) have been widely used as fluorescent emitters in blue OLEDs, but device performances are far from satisfactory. In response, we propose the concept of "nitrogen effects" endowed by doping electron-withdrawing nitrogen atoms into PAH fluorescence emitters. The presence of the n orbital on the imine nitrogen is conducive to promoting electron coupling, which leads to increased molar absorptivity and an accelerated radiative decay rate of emitters, thereby facilitating the Förster energy transfer (FET) process in the OLEDs. Additionally, electronically withdrawing nitrogen atoms enhances host-guest interactions, thereby positively affecting the FET process and the horizontal orientation factor of the emitting layer. To validate the "nitrogen effects" concept, cobalt-catalyzed multiple C-H annulation has been utilized to incorporate alkynes into the imine-based frameworks, which enables various imine-embedded PAH (IE-PAH) fluorescence emitters. The cyclization demonstrates notable regioselectivity, thereby offering a practical tool to precisely introduce peripheral groups at desired positions with bulky alkyl units positioned adjacent to the nitrogen atoms, which were previously beyond reach through the Friedel-Crafts reaction. Blue OLEDs fabricated with IE-PAHs exhibit outstanding performance with a maximum external quantum efficiency (EQEmax) of 32.7%. This achievement sets a groundbreaking record for conventional blue PAH-based fluorescent emitters, which have an EQEmax of 24.0%.

8.
Materials (Basel) ; 17(3)2024 Jan 31.
Article in English | MEDLINE | ID: mdl-38591565

ABSTRACT

With a large number of railroad and highway tunnels opening for operation, the diseases caused by hidden lining defects are increasing. The study of flow characteristics of freshly mixed concrete during tunnel lining casting is the key to revealing the formation mechanism of hidden defects. This paper revealed the location of blank lining formation by investigating the circumferential and longitudinal flow characteristics of concrete in the vault during tunnel pouring to provide suggestions for improving the quality of tunnel lining pouring for the various projects. This paper adopted the method of indoor testing, selected the suitable working conditions and flow parameters, validated the accuracy of the test with a numerical simulation, and simulated the secondary lining pouring process of the tunnel arch from the circumferential direction and longitudinal direction. This revealed the flow characteristics of the freshly mixed concrete in the process of pouring the arch lining. The flow of concrete in the arch lining was basically characterized by two major features which were similar to the flow in the pumping pipe and the layered flow. It also revealed the relationship between the concrete flow rate, flow distance, and the location of the formation of the blank lining risk zone with the slump of the concrete, the pumping pressure, and the radius of the tunnel.

9.
Materials (Basel) ; 17(8)2024 Apr 14.
Article in English | MEDLINE | ID: mdl-38673156

ABSTRACT

During the actual construction of tunnel sidewall lining, construction workers often use only one or two windows per layer for pouring in order to reduce the construction sequence, which often leads to a reduction in the quality of tunnel sidewall concrete pouring. Therefore, this study analysed the necessity of the window-by-window pouring of sidewall lining through the study of concrete flow characteristics of the tunnel sidewall lining pouring process, and the reasonable spacing of pouring windows was analysed. This study firstly verified the accuracy of the simulation parameters and the feasibility of the simulation method of the lining pouring process through indoor experiments and simulation analyses, and then it numerically simulated and analysed the flow of concrete during the lining pouring process of tunnel sidewalls. The following conclusions were made: the smaller the slump of the freshly mixed concrete, the higher the pumping flow rate; additionally, the shorter the one-time pouring distance, the smaller the spacing of the trolley feeding window should be. Furthermore, this study makes suggestions for the reasonable spacing of pouring trolleys under several working conditions.

10.
Eur J Pharmacol ; 971: 176541, 2024 May 15.
Article in English | MEDLINE | ID: mdl-38556120

ABSTRACT

Spinal cord injury (SCI), a fatal condition, is characterized by progressive tissue degradation and extreme functional deficits with limited treatment options. Hesperetin, a natural flavonoid with potent antioxidant, antiapoptotic and anti-inflammatory properties, has yet to be systematically investigated for its therapeutic effects on neurological damage in rat models of SCI. In this study, rats were given oral hesperetin once daily for 28 days, and their locomotion and histopathological changes were assessed. The findings demonstrated that hesperetin alleviates neurological damage caused by SCI. The observed behavioral improvement could be due to an increase in the survival rate of neurons and oligodendrocytes. This improvement further boosted the ability to repair tissue and form myelin after SCI, ultimately resulting in better neurological outcomes. Furthermore, the present study revealed that hesperetin possesses potent antioxidant capabilities in the context of SCI, reducing the levels of harmful oxygen free radicals and increasing the activity of antioxidant enzymes. Additionally, hesperetin markedly inhibited injury-induced apoptosis, as assessed by caspase-3 immunofluorescence staining and the expression level of caspase-3, indicating the ability of hesperetin to prevent cell death after SCI. Finally, after SCI, hesperetin treatment effectively reduced the expression of inflammatory factors, including IL-1ß, TNFα, and NF-kB, demonstrating the anti-inflammatory effect of hesperetin. Together, our results suggest that hesperetin should be considered a valuable therapeutic aid following SCI, as its positive effects on the nervous system, including antioxidant, anti-inflammatory and antiapoptotic effects, may be crucial mechanisms through which hesperetin exerts neuroprotective effects against SCI.


Subject(s)
Antioxidants , Hesperidin , Spinal Cord Injuries , Rats , Animals , Caspase 3/metabolism , Antioxidants/pharmacology , Antioxidants/therapeutic use , Antioxidants/metabolism , Apoptosis , Oxidative Stress , Anti-Inflammatory Agents/pharmacology , Anti-Inflammatory Agents/therapeutic use , Anti-Inflammatory Agents/metabolism , Spinal Cord
11.
Int J Biol Macromol ; 263(Pt 2): 130523, 2024 Apr.
Article in English | MEDLINE | ID: mdl-38428771

ABSTRACT

As a natural pH-sensing colorant, purple sweet potato anthocyanins (PSPAs) have demonstrated great potential in colorimetric film for freshness monitoring. However, the photothermal instability of PSPAs is still a challengeable issue. Herein, γ-cyclodextrin metal-organic framework (CD-MOF) loaded with PSPAs (PSPAs@CD-MOF, i.e., PM) and eugenol (EUG) were incorporated in cellulose acetate (CA) matrix for developing a smart active colorimetric film of CA/PM/EUG, where PM and EUG were hydrogen-bonded with CA. Attentions were focused on the photothermal colorimetric stability, colorimetric response, and antibacterial activity of the films. The presence of PM and EUG endowed the film outstanding UV-blocking performance and enhanced the barrier against water vapor and oxygen. Target film of CA/PM15/EUG10 had good photothermal colorimetric stability due to the protection of CD-MOF on PSPAs and the color changes with pH-stimuli were sensitive and reversible. In addition to antioxidant activity, CA/PM15/EUG10 had antibacterial activity against Escherichia coli and Staphylococcus aureus. The application trial results indicated that the CA/PM15/EUG10 was valid to indicate pork freshness and extended the shelf-life by 100 % at 25 °C, which has demonstrated a good perspective on smart active packaging for freshness monitoring and shelf-life extension.


Subject(s)
Cellulose/analogs & derivatives , Cyclodextrins , Ipomoea batatas , Metal-Organic Frameworks , Pork Meat , Red Meat , Swine , Animals , Anthocyanins/pharmacology , Colorimetry , Eugenol , Anti-Bacterial Agents/pharmacology , Escherichia coli , Food Packaging , Hydrogen-Ion Concentration
12.
J Am Chem Soc ; 146(11): 7467-7479, 2024 Mar 20.
Article in English | MEDLINE | ID: mdl-38446421

ABSTRACT

Interfacial interaction dictates the overall catalytic performance and catalytic behavior rules of the composite catalyst. However, understanding of interfacial active sites at the microscopic scale is still limited. Importantly, identifying the dynamic action mechanism of the "real" active site at the interface necessitates nanoscale, high spatial-time-resolved complementary-operando techniques. In this work, a Co3O4 homojunction with a well-defined interface effect is developed as a model system to explore the spatial-correlation dynamic response of the interface toward oxygen evolution reaction. Quasi in situ scanning transmission electron microscopy-electron energy-loss spectroscopy with high spatial resolution visually confirms the size characteristics of the interface effect in the spatial dimension, showing that the activation of active sites originates from strong interfacial electron interactions at a scale of 3 nm. Multiple time-resolved operando spectroscopy techniques explicitly capture dynamic changes in the adsorption behavior for key reaction intermediates. Combined with density functional theory calculations, we reveal that the dynamic adjustment of multiple adsorption configurations of intermediates by highly activated active sites at the interface facilitates the O-O coupling and *OOH deprotonation processes. The dual dynamic regulation mechanism accelerates the kinetics of oxygen evolution and serves as a pivotal factor in promoting the oxygen evolution activity of the composite structure. The resulting composite catalyst (Co-B@Co3O4/Co3O4 NSs) exhibits an approximately 70-fold turnover frequency and 20-fold mass activity than the monomer structure (Co3O4 NSs) and leads to significant activity (η10 ∼257 mV). The visual complementary analysis of multimodal operando/in situ techniques provides us with a powerful platform to advance our fundamental understanding of interfacial structure-activity relationships in composite structured catalysts.

13.
Indian J Pathol Microbiol ; 67(2): 466-468, 2024 Apr 01.
Article in English | MEDLINE | ID: mdl-38391381

ABSTRACT

ABSTRACT: Adult rhabdomyoma is an uncommon and benign striated muscle tumor consisting of striated muscular tissue. This neoplasm usually originates from cardiac muscle, and extracardiac rhabdomyoma is extremely rare. Herein, we report a case of adult rhabdomyoma in the lung, which has only been reported once in the 1970s. A 62-year-old woman presented to our hospital with a solid nodule on the right upper lobe. We performed tumor resection surgery and confirmed the diagnosis of adult rhabdomyoma by postoperative pathological examination. Herein, we report the clinical and pathologic characteristics of pulmonary adult rhabdomyoma (PAR) and review the literature about adult rhabdomyoma.


Subject(s)
Lung Neoplasms , Rhabdomyoma , Humans , Rhabdomyoma/pathology , Rhabdomyoma/diagnosis , Rhabdomyoma/surgery , Female , Middle Aged , Lung Neoplasms/pathology , Lung Neoplasms/diagnosis , Lung Neoplasms/surgery , Lung/pathology , Lung/diagnostic imaging , Lung/surgery , Tomography, X-Ray Computed , Immunohistochemistry
14.
Small ; 20(27): e2309932, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38295134

ABSTRACT

Recently, zeolitic imidazolate frameworks (ZIFs) composites have emerged as promising precursors for synthesizing hollow-structured N-doped carbon-based noble-metal materials with diverse structures and compositions. Here, a strong/weak competitive coordination strategy is presented for synthesizing high-performance electrocatalysts with hollow features. During the competitive coordination process, the cubic zeolitic-imidazole framework-8 (Cube-8)@ZIF-67 with core-shell structures are transformed into Cube-8@ZIF-67@PF/POM with yolk-shell nanostructures employing phosphomolybdic acid (POM) and potassium ferricyanide (PF) as the strong chelator and the weak chelator, respectively. After calcination, the hollow Mo/Fe/Co@NC catalyst exhibits superior performance in both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Interestingly, the Mo/Fe/Co@NC catalyst exhibits efficient electrocatalytic performance for Zn-air batteries (ZABs), with a high power density (≈150 mW cm-2) and superior cycling life (≈500 h) compared to commercial platinum/carbon (Pt/C) and ruthenium dioxide (RuO2) mixture benchmarks catalysts. In addition, the density functional theory further proves that after the introduction of Mo and Fe atoms, the adsorption energy with the adsorption intermediates is weakened by adjusting the d-band center, thus weakening the reaction barrier and promoting the reaction kinetics of OER. Undoubtedly, this study presents novel insights into the fabrication of ZIFs-derived hollow structure bifunctional oxygen electrocatalysts for clean-energy diverse applications.

15.
J Am Chem Soc ; 146(2): 1224-1243, 2024 Jan 17.
Article in English | MEDLINE | ID: mdl-38173272

ABSTRACT

Efficient and streamlined synthetic methods that facilitate the rapid build-up of structurally diverse π-conjugated systems are of paramount importance in the quest for organic optoelectronic materials. Among these methods, transition-metal-catalyzed oxidative Ar-H/Ar-H coupling reactions between two (hetero)arenes have emerged as a concise and effective approach for generating a wide array of bi(hetero)aryl and fused heteroaryl structures. This innovative approach bypasses challenges associated with substrate pre-activation processes, thereby allowing for the creation of frameworks that were previously beyond reach using conventional Ar-X/Ar-M coupling reactions. These inherent advantages have ushered in new design patterns for organic optoelectronic molecules that deviate from traditional methods. This ground-breaking approach enables the transcendence of the limitations of repetitive material structures, ultimately leading to the discovery of novel high-performance materials. In this Perspective, we provide an overview of recent advances in the development of organic optoelectronic materials through the utilization of transition-metal-catalyzed oxidative Ar-H/Ar-H coupling reactions. We introduce several notable synthetic strategies in this domain, covering both directed and non-directed oxidative Ar-H/Ar-H coupling strategies, dual chelation-assisted strategy and directed ortho-C-H arylation/cyclization strategy. Additionally, we shed light on the role of oxidative Ar-H/Ar-H coupling reactions in the advancement of high-performance organic optoelectronic materials. Finally, we discuss the current limitations of existing protocols and offer insights into the future prospects for this field.

16.
Acad Radiol ; 31(1): 93-103, 2024 Jan.
Article in English | MEDLINE | ID: mdl-37544789

ABSTRACT

RATIONALE AND OBJECTIVES: This study aimed to create and verify a nomogram for preoperative prediction of Ki-67 expression in breast malignancy to assist in the development of personalized treatment strategies. MATERIALS AND METHODS: This retrospective study received approval from the institutional review board and included a cohort of 197 patients with breast malignancy who were admitted to our hospital. Ki-67 expression was divided into two groups based on a 14% threshold: low and high. A radiomics signature was built utilizing 1702 radiomics features based on an intra- and peritumoral (10 mm) regions of interest. Using multivariate logistic regression, radiomics signature, and ultrasound (US) characteristics, the nomogram was developed. To evaluate the model's calibration, clinical application, and predictive ability, decision curve analysis (DCA), the calibration curve, and the receiver operating characteristic curve were used, respectively. RESULTS: The final nomogram included three independent predictors: tumor size (P = .037), radiomics signature (P < .001), and US-reported lymph node status (P = .018). The nomogram exhibited satisfactory performance in the training cohort, demonstrating a specificity of 0.944, a sensitivity of 0.745, and an area under the curve (AUC) of 0.905. The validation cohort recorded a specificity of 0.909, a sensitivity of 0.727, and an AUC of 0.882. The DCA showed the nomogram's clinical utility, and the calibration curve revealed a high consistency among the expected and detected values. CONCLUSION: The nomogram used in this investigation can accurately predict Ki-67 expression in people with malignant breast tumors, helping to develop personalized treatment approaches.


Subject(s)
Breast Neoplasms , Nomograms , Humans , Female , Ki-67 Antigen , Radiomics , Retrospective Studies , Breast Neoplasms/diagnostic imaging , Breast Neoplasms/surgery
17.
Small ; 20(15): e2304574, 2024 Apr.
Article in English | MEDLINE | ID: mdl-38009795

ABSTRACT

Direct selective transformation of greenhouse methane (CH4) to liquid oxygenates (methanol) can substitute energy-intensive two-step (reforming/Fischer-Tropsch) synthesis while creating environmental benefits. The development of inexpensive, selective, and robust catalysts that enable room temperature conversion will decide the future of this technology. Single-atom catalysts (SACs) with isolated active centers embedded in support have displayed significant promises in catalysis to drive challenging reactions. Herein, high-density Ni single atoms are developed and stabilized on carbon nitride (NiCN) via thermal condensation of preorganized Ni-coordinated melem units. The physicochemical characterization of NiCN with various analytical techniques including HAADF-STEM and X-ray absorption fine structure (XAFS) validate the successful formation of Ni single atoms coordinated to the heptazine-constituted CN network. The presence of uniform catalytic sites improved visible absorption and carrier separation in densely populated NiCN SAC resulting in 100% selective photoconversion of (CH4) to methanol using H2O2 as an oxidant. The superior catalytic activity can be attributed to the generation of high oxidation (NiIII═O) sites and selective C─H bond cleavage to generate •CH3 radicals on Ni centers, which can combine with •OH radicals to generate CH3OH.

18.
Small ; 20(22): e2310266, 2024 May.
Article in English | MEDLINE | ID: mdl-38098346

ABSTRACT

The interactions between the catalyst and support are widely used in many important catalytic reactions but the construction of strong interaction with definite microenvironments to understand the structure-activity relationship is still challenging. Here, strongly-interacted composites are prepared via selective exsolution of active NiSe2 from the host matrix of NiFe2O4 (S-NiSe2/NiFe2O4) taking advantage of the differences of migration energy, in which the NiSe2 possessed both high dispersion and small size. The characteristics of spatially resolved scanning transmission X-ray microscopy (STXM) coupled with analytical Mössbauer spectra for the surface and bulk electronic structures unveiled that this strongly interacted composite triggered more charge transfers from the NiSe2 to the host of NiFe2O4 while stabilizing the inherent atomic coordination of NiFe2O4. The obtained S-NiSe2/NiFe2O4 exhibits overpotentials of 290 mV at 10 mA cm-2 for oxygen evolution reaction (OER). This strategy is general and can be extended to other supported catalysts, providing a powerful tool for modulating the catalytic performance of strongly-interacted composites.

19.
iScience ; 26(12): 108435, 2023 Dec 15.
Article in English | MEDLINE | ID: mdl-38077124

ABSTRACT

Layered double hydroxides (LDHs) are widely used in catalytic field, especially in photocatalysis, benefiting from the ultrathin 2D structure and luxuriant surface functional groups. However, the wide band gap and low utilization rate of solar spectrum affect their photocatalytic performance. Herein, we integrated n-type CoAl-LDH with p-type Cu2O nanoparticles to construct a p-n heterojunction with a strong built-in electric field, which can prevent photoinduced electron-hole pairs from recombination as well as facilitate charge transfer. With the X-ray photoelectron spectroscope and in situ Fourier transform infrared spectroscopy, we confirmed the charge transfer under light illumination complying with the type II-scheme mechanism and analyzed the intermediates during photocatalytic CO2 reduction reaction (CO2RR). The highest yields reached 320.9 µmol h-1 g-1 for CoAl-LDH@Cu2O-60 (LC-60) under 1 h light irradiation, which was about 1.6 times than the pristine CoAl-LDH. The sample also exhibited excellent stability which maintained 84.1% of initial performance after 4 circulations.

20.
Nat Commun ; 14(1): 6142, 2023 Oct 05.
Article in English | MEDLINE | ID: mdl-37798263

ABSTRACT

Electrocatalytic CO2 reduction into value-added multicarbon products offers a means to close the anthropogenic carbon cycle using renewable electricity. However, the unsatisfactory catalytic selectivity for multicarbon products severely hinders the practical application of this technology. In this paper, we report a cascade AgCu single-atom and nanoparticle electrocatalyst, in which Ag nanoparticles produce CO and AgCu single-atom alloys promote C-C coupling kinetics. As a result, a Faradaic efficiency (FE) of 94 ± 4% toward multicarbon products is achieved with the as-prepared AgCu single-atom and nanoparticle catalyst under ~720 mA cm-2 working current density at -0.65 V in a flow cell with alkaline electrolyte. Density functional theory calculations further demonstrate that the high multicarbon product selectivity results from cooperation between AgCu single-atom alloys and Ag nanoparticles, wherein the Ag single-atom doping of Cu nanoparticles increases the adsorption energy of *CO on Cu sites due to the asymmetric bonding of the Cu atom to the adjacent Ag atom with a compressive strain.

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