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1.
ACS Sens ; 9(6): 3187-3197, 2024 Jun 28.
Article in English | MEDLINE | ID: mdl-38809143

ABSTRACT

Ultrasensitive photoelectric detection of nitrogen dioxide (NO2) with PHI under visible light irradiation at room temperature (RT) remains an ongoing challenge due to the low charge separation and scarce adsorption sites. In this work, a dimensionally matched ultrathin CoNiHHTP MOF/PHI Z-scheme heterojunction is successfully constructed by taking advantage of the π-π interactions existing between the CoNiHHTP MOF and PHI. The amount-optimized heterojunction possesses a record detection limit of 1 ppb (response = 15.6%) for NO2 under 405 nm irradiation at RT, with reduced responsive (3.6 min) and recovery (2.7 min) times, good selectivity and reversibility, and long-time stability (150 days) compared with PHI, even superior to others reported at RT. Based on the time-resolved photoluminescence spectra, in situ X-ray photoelectron spectra, and diffuse reflectance infrared Fourier transform spectroscopy results, the resulting sensing performance is attributed to the favorable Z-scheme charge transfer and separation. Moreover, the Ni nodes favorably present in adjacent metal sites between the lamellae contribute to charge transfer and redistribution, whereas Co nodes could act as selective centers for promoted adsorption of NO2. Interestingly, it is confirmed that the CoNiHHTP MOF/PHI heterojunction could effectively reduce the influence of O2 in the gas-sensitive reaction due to their unique bimetallic (Co and Ni) nodes, which is also favorable for the improved sensing performances for NO2. This work provides a feasible strategy to develop promising PHI-based optoelectronic gas sensors at RT.


Subject(s)
Metal-Organic Frameworks , Nitrogen Dioxide , Nitrogen Dioxide/analysis , Nitrogen Dioxide/chemistry , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/radiation effects , Light , Limit of Detection , Temperature
2.
Opt Express ; 32(4): 5206-5213, 2024 Feb 12.
Article in English | MEDLINE | ID: mdl-38439252

ABSTRACT

Artificially designed metamaterial structures can manipulate electromagnetic waves, endowing them with exotic physical properties that are not found in natural materials, such as negative refractive index, superlens, and inverse Doppler effect. These characteristics are widely applied in various engineering and military applications. Due to increasingly complex application environments and innovation in radar detection technology, the combination of broadband absorption performance under thin thickness and efficient preparation methods at low cost is often the focus of research on new generation stealth materials. Here, we propose Al@SiO2 composite conductive film metamaterial (Al@SiO2 CCFM) to achieve wideband absorption of electromagnetic waves. This metamaterial structure combines two resonant units, resulting in three absorption bands in the absorption curve. The results show that the absorption rate of the metamaterial is above 90% in the frequency range of 10.6 GHz to 26.0 GHz. The resonance mechanism between multiple structures is a prerequisite for achieving wideband absorption. The materials Al and SiO2 used in Al@SiO2 CCFM are inexpensive and abundant, and the fabrication method is simple. Therefore, they hold great potential for large-scale applications in the multispectral stealth and electromagnetic shielding field.

3.
Sensors (Basel) ; 24(2)2024 Jan 05.
Article in English | MEDLINE | ID: mdl-38257406

ABSTRACT

To improve the classification of pig vocalization using vocal signals and improve recognition accuracy, a pig vocalization classification method based on multi-feature fusion is proposed in this study. With the typical vocalization of pigs in large-scale breeding houses as the research object, short-time energy, frequency centroid, formant frequency and first-order difference, and Mel frequency cepstral coefficient and first-order difference were extracted as the fusion features. These fusion features were improved using principal component analysis. A pig vocalization classification model with a BP neural network optimized based on the genetic algorithm was constructed. The results showed that using the improved features to recognize pig grunting, squealing, and coughing, the average recognition accuracy was 93.2%; the recognition precisions were 87.9%, 98.1%, and 92.7%, respectively, with an average of 92.9%; and the recognition recalls were 92.0%, 99.1%, and 87.4%, respectively, with an average of 92.8%, which indicated that the proposed pig vocalization classification method had good recognition precision and recall, and could provide a reference for pig vocalization information feedback and automatic recognition.


Subject(s)
Cough , Recognition, Psychology , Swine , Animals , Neural Networks, Computer , Principal Component Analysis
4.
Sci Rep ; 14(1): 1247, 2024 Jan 13.
Article in English | MEDLINE | ID: mdl-38218745

ABSTRACT

Traffic time series anomaly detection has been intensively studied for years because of its potential applications in intelligent transportation. However, classical traffic anomaly detection methods often overlook the evolving dynamic associations between road network nodes, which leads to challenges in capturing the long-term temporal correlations, spatial characteristics, and abnormal node behaviors in datasets with high periodicity and trends, such as morning peak travel periods. In this paper, we propose a mirror temporal graph autoencoder (MTGAE) framework to explore anomalies and capture unseen nodes and the spatiotemporal correlation between nodes in the traffic network. Specifically, we propose the mirror temporal convolutional module to enhance feature extraction capabilities and capture hidden node-to-node features in the traffic network. Morever, we propose the graph convolutional gate recurrent unit cell (GCGRU CELL) module. This module uses Gaussian kernel functions to map data into a high-dimensional space, and enables the identification of anomalous information and potential anomalies within the complex interdependencies of the traffic network, based on prior knowledge and input data. We compared our work with several other advanced deep-learning anomaly detection models. Experimental results on the NYC dataset illustrate that our model works best compared to other models for traffic anomaly detection.

5.
Small ; 19(49): e2304084, 2023 Dec.
Article in English | MEDLINE | ID: mdl-37612797

ABSTRACT

Although the electron-withdrawing effect of gold (Au) is highlighted in catalytic reactions, its enhancement mechanism for electron transport, especially in the electrochemical process, is still unclear. Herein, Au-decorated Bi2 O3 (Au-Bi2 O3 ) is proposed as a proof-of-concept to investigate the electron-withdrawing effect in the electrocatalytic CO2 reduction reaction (eCO2 RR) process. Evidence from in situ Raman spectra and in situ XRD tests reveals that, compared to Bi2 O3 , Bi species in Au-Bi2 O3 can be reduced to metallic Bi more rapidly and more easily driven by the electron-withdrawing effect of Au. The XPS tests after eCO2 RR further validates the transformation from Bi3+ to Bi0 in Au-Bi2 O3 is more complete. Meanwhile, in the in situ Fourier transform infrared (FTIR) spectra, the key intermediates (CO2 *- and OCHO*- ) appear at the more positive potential, indicating that metallic Bi is favorable for eCO2 RR due to the lower energy barrier as corroborated by density function theory (DFT) calculations. Au don't directly participate in the conversion from CO2 to formate as the reaction sites, but utilize the electron-withdrawing effect to motivate Bi-sites to deliver higher catalytic activity and higher selectivity to formate at a lower applied potential. This study not only has an insight into the electron-withdrawing effect of Au on the eCO2 RR process, but also develops a new perspective for engineering electron-withdrawing effect in electrocatalysts for high-efficient CO2 -to-formate conversion.

6.
Small ; 19(39): e2302025, 2023 Sep.
Article in English | MEDLINE | ID: mdl-37231554

ABSTRACT

The renewable electricity-driven hydrogen evolution reaction (HER) coupled with biomass oxidation is a powerful avenue to maximize the energy efficiency and economic feedback, but challenging. Herein, porous Ni-VN heterojunction nanosheets on nickel foam (Ni-VN/NF) are constructed as a robust electrocatalyst to simultaneously catalyze HER and 5-hydroxymethylfurfural electrooxidation reaction (HMF EOR). Benefiting from the surface reconstruction of Ni-VN heterojunction during the oxidation process, the derived NiOOH-VN/NF energetically catalyzes HMF into 2,5-furandicarboxylic acid (FDCA), yielding the high HMF conversion (>99%), FDCA yield (99%), and Faradaic efficiency (>98%) at the lower oxidation potential along with the superior cycling stability. Ni-VN/NF is also surperactive for HER, exhibiting an onset potential of ≈0 mV and Tafel slope of 45 mV dec-1 . The integrated Ni-VN/NF||Ni-VN/NF configuration delivers a compelling cell voltage of 1.426 V at 10 mA cm-2 for the H2 O-HMF paired electrolysis, about 100 mV lower than that for water splitting. Theoretically, for Ni-VN/NF, the superiority in HMF EOR and HER is mainly dominated by the local electronic distribution at the heterogenous interface, which accelerates the charge transfer and optimize the adsorption of reactants/intermediates by modulating the d-band center, therefore being an advisable thermodynamic and kinetic process.

7.
Molecules ; 28(7)2023 Mar 29.
Article in English | MEDLINE | ID: mdl-37049803

ABSTRACT

The renewable-energy-driven integration of hydrogen production and biomass conversion into value-added products is desirable for the current global energy transition, but still a challenge. Herein, carbon-coated CoO-Co heterojunction arrays were built on copper foam (CoO-Co@C/CF) by the carbothermal reduction to catalyze the hydrogen evolution reaction (HER) coupled with a 5-hydroxymethylfurfural electrooxidation reaction (HMFEOR). The electronic modulation induced by the CoO-Co heterojunction endows CoO-Co@C/CF with a powerful catalytic ability. CoO-Co@C/CF is energetic for HER, yielding an overpotential of 69 mV at 10 mA·cm-1 and Tafel slope of 58 mV·dec-1. Meanwhile, CoO-Co@C/CF delivers an excellent electrochemical activity for the selective conversion from HMF into 2,5-furandicarboxylic acid (FDCA), achieving a conversion of 100%, FDCA yield of 99.4% and faradaic efficiency of 99.4% at the lower oxidation potential, along with an excellent cycling stability. The integrated CoO-Co@C/CF||CoO-Co@C/CF configuration actualizes the H2O-HMF-coupled electrolysis at a satisfactory cell voltage of 1.448 V at 10 mA·cm-2. This work highlights the feasibility of engineering double active sites for the coupled electrolytic system.

8.
Small ; 19(4): e2204889, 2023 Jan.
Article in English | MEDLINE | ID: mdl-36420939

ABSTRACT

Exquisite design of RuO2 -based catalysts to simultaneously improve activity and stability under harsh conditions and reduce the Ru dosage is crucial for advancing energy conversion involving oxygen evolution reaction (OER). Herein, a distinctive cobalt-doped RuOx framework is constructed on Co3 O4 nanocones (Co3 O4 @CoRuOx ) as a promising strategy to realize above urgent desires. Extensive experimental characterization and theoretical analysis demonstrate that cobalt doped in RuOx lattice brings the oxygen vacancies and lattice contraction, which jointly redistribute the electron configuration of RuOx . The optimized d-band center balances the adsorption energies of oxygenated intermediates, lowing the thermodynamical barrier of the rate-determining step; and meanwhile, the over-oxidation and dissolution of Ru species are restrained because of the p-band down-shifting of the lattice oxygen. Co3 O4 @CoRuOx with 3.7 wt.% Ru delivers the extremely low OER overpotentials at 10 mA cm-2 in alkaline (167 mV), neutral (229 mV), and acidic electrolytes (161 mV), and super operating stability over dozens of hours. The unprecedented activity ranks first in all pH-universal OER catalysts reported so far. These findings provide a route to produce robust low-loading Ru catalysts and an engineering approach for regulating the central active metal through synergy of co-existing defects to improve the catalytic performance and stability.

9.
ACS Nano ; 16(5): 7794-7803, 2022 May 24.
Article in English | MEDLINE | ID: mdl-35435674

ABSTRACT

The "Fe effect" can maximize the activity of nickel-iron layered double hydroxides (NiFe-LDH) toward oxygen evolution reaction (OER) when the iron content, the lattice distortion, the conductivity, and other related factors are well balanced. It is difficult for the homogeneous NiFe-LDH to take good care of the above requirements at the same time. Herein, we proposed an elaborate atmosphere corrosion strategy to construct porous NiFe-LDH with rich edge/surface-Fe defects on Ni foam (NF). Such edge/surface-Fe defects, mainly caused by the local unequal-stoichiometric ratio of Fe/Ni in the nanometer or subnanometer region, are determined by the unbalanced permeating of the acid vapor and the confined reaction of local Fe and Ni species ionized by the acid vapor. Benefiting from the abundant and fantastic edge/surface-Fe defects, the optimal NiFe-LDH prepared by atmosphere corrosion is more energetic for OER than that synthesized in conventional liquid phase, only a potential of 1.481 and 1.552 VRHE to respectively achieve the current density of 100 and 1000 mA cm-2 as well as a satisfactory stability and reproducibility. An overall water-splitting system assembled by inhomogeneous NiFe-LDH and commercial Pt-C can reach a current density of 100 mA cm-2 at a solar cell of 1.72 V. Additionally, the atmosphere corrosion is very suitable for the large-scale, green, and economic synthesis of metal-based catalysts with high enrichment of defects, highlighting its potential for device and industrial applications.

10.
Chemosphere ; 293: 133532, 2022 Apr.
Article in English | MEDLINE | ID: mdl-34995622

ABSTRACT

The electro-Fenton oxidation is one of the powerful approaches for achieving the complete mineralization of organic pollutants in water. The key dilemma for efficient industrial application of electro-Fenton oxidation is the complicated post-processing of iron sludge, and the cost and risk associated with H2O2 transportation and storage. Herein, Cu-coupled Fe/Fe3C covered with carbon layer on carbon felt (Cu-Fe/Fe3C@C), engineered by a hydrothermal reaction followed by the consequent thermal-treatment in N2 atmosphere, as a self-supported integrated cathode were used for an onsite oxygen reduction reaction and a Fenton oxidation reaction. Experimental evidences demonstrate that, at the operating potential of -1.1 V, Fe3C can selectively catalyze O2 into H2O2 by 2e reduction pathways with assistance of metal Cu. Meanwhile, metal Fe and Cu incorporated into Cu-Fe/Fe3C@C simultaneously motivate the onsite Fenton oxidation arose by H2O2. Such a win-win catalyst presented high activity in the electro-Fenton process. In acidic environment, the efficient mineralization rate of methylene blue, nitrobenzene, phenol, and bisphenol A can reach more than 70% in 60 min, as well as the excellent stability and durability due to the protection of graphited carbon layer. Compared with tradition electrochemical degrade system, the prepared Cu-Fe/Fe3C@C electrode as cathode for practical refractory brewing leachate treatment reveal more efficient decolorization and mineralization, saving 14.3% of electricity.


Subject(s)
Hydrogen Peroxide , Water Pollutants, Chemical , Carbon , Catalysis , Electrodes , Iron , Oxidation-Reduction , Water Pollutants, Chemical/analysis
11.
Zhongguo Zhong Yao Za Zhi ; 47(24): 6607-6614, 2022 Dec.
Article in Chinese | MEDLINE | ID: mdl-36604909

ABSTRACT

This study aimed to improve the transdermal permeation quantity of Baimai Ointment by investigating the enhancing effects of physical and chemical permeation promoting methods on transdermal permeation of Baimai Ointment. The improved Franz diffusion cell method was used for in vitro transdermal experiment. The abdominal skin of mice was used, and the skin was treated with 3% propylene glycol in the chemical enhancement group. Ultrasonic technology was introduced in the physical enhancement group. The conditions of ultrasonic technology were optimized by single factor trial. Taking Q_(EF) and ER as the indexes of penetration promotion performance, the enhancing effects of the two methods were compared. The results showed that the promotion performance of 3% propylene glycol for ammonium glycyrrhizinate, nardosinone and curcumin of the chemical enhancement group were 1.74, 1.60, and 3.73 times higher than those of the blank group, respectively. The overall permeation efficiency of the Baimai Ointment was significantly improved. The comprehensive promoting effect on each component was curcumin>ammonium glycyrrhizinate>nardosinone. In the physical enhancement group, the penetration promoting effect of ultrasonic power 1.0 W was better than that of 2.0 W and 0.5 W, ultrasonic time 5 min was better than 3 min and 8 min, and the ultrasonic frequency 1 MHz was better than 3 MHz. Therefore, the optimal ultrasonic condition was 1.0 W-5 min-1 MHz. Under this condition, in terms of the transdermal permeation for ammonium glycyrrhizinate, the Q_(EF) and ER of the ultrasonic technology were better than those of 3% propylene glycol. In terms of the transdermal permeation for nardosinone and curcumin, the QEF and ER of 3% propylene glycol were better than those of the ultrasonic technology. Therefore, 3% propylene glycol combined with ultrasonic technology can be used to promote permeation of Baimai Ointment that contains both water-soluble and fat-soluble components in the clinical application. This study provides a theoretical basis for the clinical application of Baimai Ointment and other transdermal preparations.


Subject(s)
Ammonium Compounds , Curcumin , Mice , Animals , Skin Absorption , Curcumin/pharmacology , Ultrasonics , Administration, Cutaneous , Skin , Propylene Glycol/metabolism , Propylene Glycol/pharmacology , Ammonium Compounds/metabolism , Ammonium Compounds/pharmacology , Permeability
12.
ChemSusChem ; 14(24): 5508-5516, 2021 Dec 17.
Article in English | MEDLINE | ID: mdl-34652074

ABSTRACT

Although the activity of electrocatalysts towards oxygen evolution reaction (OER) has achieved considerable improvement by modulating the intrinsic electron structure, the role of supports to OER performance, often being reduced to enhancing the conductivity, is not fully explored. In this paper, a proof-of-concept study based on a series of hybrids of nickel iron (hydr)oxide nanoparticles (NiFeO NPs) and carbon supports with different oxidation level compared the motivation of supports for OER activity. The key to implementation lay in anchoring and growing of NiFeO NPs on the various carbon supports by electrostatic assembly and subsequent in-situ reduction. A series of experiments indicated that the strong coupling of metal ions and graphene oxide (GO) contributed to the formation of ultrasmall NiFeO NPs (≈2 nm) and the firm interaction between NiFeO NPs and GO, which in turn resulted in exposing more metal atoms, modulating local electron structure of active sites, and accelerating the charge-transfer ability. The OER activity of optimal NiFeO NPs anchored on rGO (NiFeO NPs/rGO) was significantly elevated, achieving an overpotential as small as 201 mV at 10 mA cm-2 and a low Tafel slope of 68 mV dec-1 , as well as remarkable stability. Such exciting capacity for catalyzing OER prevailed over the vast majority of previously reported transition-metal electrocatalysts, even superior to numerous noble metal-containing catalysts. The electrolyzer employing NiFeO NPs/rGO and commercial Pt/C for anode and cathode could be powered by a solar cell for efficient alkaline seawater splitting. This work opens up a universal and scalable way for further advancing the intrinsic activity of energy-related materials.

13.
Sci Bull (Beijing) ; 66(3): 275-283, 2021 Feb 15.
Article in English | MEDLINE | ID: mdl-36654333

ABSTRACT

Efficient charge separation and rapid interfacial reaction kinetics are crucial factors that determine the efficiency of photocatalytic hydrogen evolution. Herein, a fascinating 2D heterojunction photocatalyst with superior photocatalytic hydrogen evolution performance - holey C3N4 nanosheets nested with TiO2 nanocrystals (denoted as HCN/TiO2) - is designed and fabricated via an in situ exfoliation and conversion strategy. The HCN/TiO2 is found to exhibit an ultrathin 2D heteroarchitecture with intimate interfacial contact, highly porous structures and ultrasmall TiO2 nanocrystals, leading to drastically improved charge carrier separation, maximized active sites and the promotion of mass transport for photocatalysis. Consequently, the HCN/TiO2 delivers an impressive hydrogen production rate of 282.3 µmol h-1 per 10 mg under AM 1.5 illumination and an apparent quantum efficiency of 13.4% at a wavelength of 420 nm due to the synergetic enhancement of surface reactions and charge separation. The present work provides a promising strategy for developing high-performance 2D heterojunctions for clean energy applications.

14.
Angew Chem Int Ed Engl ; 59(10): 4154-4160, 2020 Mar 02.
Article in English | MEDLINE | ID: mdl-31863720

ABSTRACT

Even though transition-metal phosphides (TMPs) have been developed as promising alternatives to Pt catalyst for the hydrogen evolution reaction (HER), further improvement of their performance requires fine regulation of the TMP sites related to their specific electronic structure. Herein, for the first time, boron (B)-modulated electrocatalytic characteristics in CoP anchored on the carbon nanotubes (B-CoP/CNT) with impressive HER activities over a wide pH range are reported. The HER performance surpasses commercial Pt/C in both neutral and alkaline media at large current density (>100 mA cm-2 ). A combined experimental and theoretical study identified that the B dopant could reform the local electronic configuration and atomic arrangement of bonded Co and adjacent P atoms, enhance the electrons' delocalization capacity of Co atoms for high electrical conductivity, and optimize the free energy of H adsorption and H2 desorption on the active sites for better HER kinetics.

15.
Chinese Journal of School Health ; (12): 704-708, 2020.
Article in Chinese | WPRIM (Western Pacific) | ID: wpr-821930

ABSTRACT

Objective@#To analyze Internet behaviors of children and adolescents and their influencing factors, and to provide scientific basis for health education guidance and prevention measures.@*Methods@#A stratified cluster sampling method was used. From January to June 2019, 30 955 primary school students in 16 provinces (municipalities), from eastern, central, and western economic zones of China were selected to conduct a questionnaire survey, regarding general demographics, diet and exercise, tobacco, alcohol and sleep, Internet and electronics usage, etc.@*Results@#Among them, 43.1% of students had never been online with girls (44.7%) higher than boys (41.8%)(χ2=21.04, P<0.01); 1.3% of students reported online time for more than 4 hours a day, boys were significantly higher than girls(χ2=15.87, P<0.01); Internet addiction was detected in 2.4% of elementary school students, with boys (3.0%) higher than girls(1.7%)(χ2=331.77, P<0.01), and the trend increases with grade. With sixth grade (3.3%) were significantly higher than children from the first grade (0.8%) and other grades(χ2=163.96, P<0.01). Children’s tendency to Internet addiction was 11.9%, of which boys were 13.0% and girls were 10.6%, boys were significantly higher than girls(χ2=117.66, P<0.01). Pearson correlation analysis revealed that, after controlling gender age, boarding school, family relationship, single parents and regrouped families, smoking, drinking sugary drinks, eating fried foods, and left-behind were positively related to Intenet addiction(r=0.06, 0.07, 0.27, 0.44, 0.07, 0.11, 0.09, P<0.01), while medium and high intensity sports, effective physical education, health education in school, AIDS education and parental restrictions on TV and computer games, were negatively associated with internet addiction(r=-0.74, -0.65, -0.04, -0.05, -0.63, P<0.01).@*Conclusion@#The internet addiction of Chinese primary school students is common and increases by year. High-intensity, high-density sports, effective physical education, and health education could help prevent Internet addiction among children.

16.
Nanoscale ; 11(47): 23027-23034, 2019 Dec 21.
Article in English | MEDLINE | ID: mdl-31774093

ABSTRACT

Nanostructure engineering of heteroatom-doped carbon catalysts can greatly enhance their electrocatalytic activity by increasing the accessible active sites and beneficial physical properties (e.g., surface area, conductivity, etc.). Herein, we successfully constructed ultra-thin N,P co-doped carbon (NPC) on the surface of multi-walled carbon nanotubes (CNT) by using phytic acid (PA) as a "guide". The rich phosphate groups in PA allow them to be covalently modified on the surface of CNT by the condensation reaction and to further attract large aniline monomers through acid-base interactions, resulting in the uniform and tight bonding between polyaniline and CNT after the polymerization process. During the subsequent thermal reaction, PA also serves as a self-sacrificial dopant for the formation of ultra-thin NPC and the doping amount of P in NPC can be easily adjusted by changing the amount of PA. Due to the abundance of active sites, large electrochemically active surface area and rapid electron transfer, the developed CNT@NPC presents remarkable electrocatalytic activities for the hydrogen evolution reaction (HER) with an overpotential of 167, 440 and 304 mV to reach a current density of 10 mA cm-2 in acidic, neutral, and alkaline electrolytes, respectively. In particular, its acidic HER activity exceeds that of most reported metal-free electrocatalysts and is comparable to that of some excellent transition metal-based catalysts. The approach proposed here is of potential importance for the preparation of ideal heteroatom-doped carbon/nanocarbon composites for use in a variety of future energy conversion systems.

17.
Chem Commun (Camb) ; 55(67): 10011-10014, 2019 Aug 15.
Article in English | MEDLINE | ID: mdl-31378801

ABSTRACT

The doping amount of heteroatoms in N, S co-doped carbon nanotubes (CNT-NS) was accurately and extensively regulated by retarding pyrolysis-gas diffusion. The effect of the content of N and S on the hydrogen evolution activity of CNT-NS was revealed for the first time both experimentally and theoretically.

18.
ChemSusChem ; 12(14): 3304-3311, 2019 Jul 19.
Article in English | MEDLINE | ID: mdl-31144453

ABSTRACT

Electrochemical conversion of CO2 into syngas, which can be used directly in the classical petroleum industrial processes, provides a powerful approach for achieving the recycling of anthropogenic carbon. Pd has previously been reported to be capable of converting CO2 into syngas with various CO/H2 ratios, but only at limited applied potential, which is mainly attributed to fewer active sites exposed toward electrocatalysis. Herein, high-performance Pd nanomeshes (NMs) assembled with branch-like Pd nanoparticles were designed and synthesized by using a simple interface-induced self-assembly strategy; these NMs could catalyze CO2 -into-syngas conversion with a high current density in a wide applied potential range from -0.5 to -1.0 V (vs. reversible hydrogen electrode). Further evidence validated that the enhanced activity of the Pd NMs was not only caused by the crosslinked network structure accelerating electron transport, but also by the greater number of edge and/or corner active sites exposed on the surface of the NMs, which facilitated CO2 adsorption, CO2 .- formation, COOH* stabilization, and CO generation. Under optimal operating conditions, Pd NMs could balance two competing reactions: CO2 reduction and hydrogen evolution. The resultant syngases with the ideal and tunable CO/H2 ratio between 0.5:1 and 1:1 could be used directly for methanol synthesis and Fischer-Tropsch reactions.

19.
Nanoscale ; 10(23): 10971-10978, 2018 Jun 14.
Article in English | MEDLINE | ID: mdl-29855010

ABSTRACT

Electrochemical oxygen evolution reaction (OER) can be accelerated by employing transition-metal-based catalysts to obtain the desired activity and durability. Considering the promoting effect of the electrode structure on catalyzing OER, a stereo-film on carbon cloth comprising FeNi3 nanosheet-covered FeOOH (F@FeNi3-CC) was engineered by the hydrothermal reaction and subsequent synchronous electrodeposition of Fe and Ni ions. In F@FeNi3-CC, the FeOOH array not only provides the Fe source of FeNi3 nanosheets during the cathodic electrodeposition, but also functions as the support for the ultrathin FeNi3 nanosheets. Such a stereo-film with good electrolyte-permeability also offers expedited electrolyte/reactant transmission paths. The tailored FeNi3 nanosheet offers abundant exposed catalytic sites by virtue of the in situ derived hydroxide layer during anodic oxidation and also acts as the current collector to accelerate charge transport. The F@FeNi3-CC electrode yields outstanding catalytic activity towards OER in alkaline media, particularly at low potential of 1.50 V and large current density of 100 mA cm-2, accompanied with the excellent long-term stability. These results are significant for the construction of stereo-film electrodes for various engineering applications.

20.
Small ; 14(25): e1800763, 2018 Jun.
Article in English | MEDLINE | ID: mdl-29806149

ABSTRACT

Fabricating cost-effective, bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in basic media is critical for renewable energy generation. Here, NiSe/CP, Ni0.85 Se/CP, and NiSe-Ni0.85 Se/CP heterostructure catalysts with different phase constitutions are successfully prepared through in situ selenylation of a NiO nanoflake array oriented on carbon paper (CP) by tuning the original Ni/Se molar ratio of the raw materials. The relationship between the crystal phase component and electrocatalytic activity is systematically studied. Benefiting from the synergetic effect of the intrinsic metallic state, facile charge transport, abundant catalytic active sites, and multiple electrolyte transmission paths, the optimized NiSe-Ni0.85 Se/CP exhibits a remarkably higher catalytic activity for both the HER and OER than single-phase NiSe/CP and Ni0.85 Se/CP. A current density of 10 mA cm-2 at 1.62 V and a high stability can be obtained by using NiSe-Ni0.85 Se/CP as both the cathode and anode for overall water splitting under alkaline conditions. Density functional theory calculations confirm that H and OH- can be more easily adsorbed on NiSe-Ni0.85 Se than on NiSe and Ni0.85 Se. This study paves the way for enhancing the overall water splitting performance of nickel selenides by fabricating heterophase junctions using nickel selenides with different phases.

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