30 November 2022, Volume 53 Issue 11

    

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Focuses & Concerns (The Project of Chongqing Press Fund in 2021)
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  Study on vehicle-mounted methanol reforming in-situ hydrogen production high-throughput catalyst

  Jorunal of Functional Materials. 2022, 53(11): 11001-11006. https://doi.org/10.3969/j.issn.1001-9731.2022.11.001

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  Under the background of carbon dioxide emissions peak and carbon dioxide neutrality target, clean and efficient hydrogen fuel cell vehicles have broad development prospects. Methanol is a renewable, low-cost green fuel. Methanol and fuel cell combined to form mobile power generation equipment, has the advantages of less carbon emissions, fast fuel filling, easy storage and transportation. The vehicle-mounted methanol reforming in-situ hydrogen production technology solves the problems of hydrogen storage and transportation, weak safety and low hydrogen storage rate. Three methods of hydrogen production including methanol pyrolysis, methanol steam reforming and methanol partial oxidation were summarized. Methanol steam reforming is an effective way to produce hydrogen for hydrogen fuel vehicles due to its fast hydrogen production rate and low carbon monoxide content in tail gas. The characteristics and development status of Cu, Zn-Cr, Ni and noble metal catalysts for hydrogen production by methanol reforming were reviewed. The effects of different properties on methanol conversion, hydrogen production rate and near-zero CO selectivity of catalysts were discussed from the aspects of elemental composition, ratio and preparation method. In the future, the development of new catalysts with high stability, high catalytic activity, low cost, high-throughput and near-zero CO selectivity is an important direction for the development of vehicle-mounted methanol reforming hydrogen production.
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  Research on CO-SCR performance of reducible oxide supported copper-based catalysts

  Jorunal of Functional Materials. 2022, 53(11): 11007-11014. https://doi.org/10.3969/j.issn.1001-9731.2022.11.002

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  Environmental friendly copper oxides were supposed as the potential CO-SCR denitrification catalysts due to the suitable redox capacity. Despite that, sintering at higher temperature and the poor dispersity and stability of CuO_x species remain the main factor to restrict their further application. Generally, the high dispersion of copper species could be achieved via the coordinated combination of copper oxides and appropriate supports, thus overcoming the present disadvantages of copper-based oxides and improving catalytic activity. Based on this, herein, the reducible oxides (CeO₂, γ-Fe₂O₃) were selected as the support, where the CuO_x/CeO₂ and CuO_x/γ-Fe₂O₃ catalysts (loading capacity of CuO was 2.5wt%) were prepared by traditional impregnation method, and the pure CuO was selected as the reference catalyst. Meanwhile, the influence of reducible support on the physicochemical properties and denitrification performance of copper-based catalyst was systematically studied. The results displayed that the introduction of the support improved the catalytic activity of copper oxides to some extent, where the CuO_x/CeO₂ catalyst with CeO₂ as support not only showed better SCR catalytic activity, higher N₂ selectivity, but also possessed the wider temperature window of activity. In addition, serious of characterizations (XRD, H₂-TPR, NO-TPD, SEM+EDX-Mapping, XPS, In situ DRIFTs and so on) analysis revealed that compared with γ-Fe₂O₃, introducing CeO₂ as the support was more conducive to improve the dispersion of CuO_x species, optimize the valence distribution of CuO_x species, as well as increase the surface active site. This work may serve as an important reference for fabricating Cu-based catalyst supported on reducible oxide with superior performance in potential applications for CO-SCR.
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  Introduction and characterization of vacancies in semiconductor materials and their influence on photocatalysis

  Jorunal of Functional Materials. 2022, 53(11): 11015-11022. https://doi.org/10.3969/j.issn.1001-9731.2022.11.003

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  Photocatalysis is considered to be one of the effective methods to solve the global energy crisis and environmental pollution problems. However, the low energy conversion efficiency of photocatalyst inhibits the application of photocatalysis. Vacancy is the most common crystal defect, because it can regulate the electronic structure and surface properties of photocatalyst without introducing external elements, and promote the light absorption, charge separation and migration of photocatalyst and surface reaction. Therefore, this review summarizes the latest progress of vacancy defects in photocatalysis. Firstly, some primary methods for introducing vacancy defects in photocatalyst are discussed, including common methods such as chemical reduction and high temperature treatment, and uncommon but effective methods such as hydrolysis and ultrasound. Secondly, the current characterization techniques for identifying and quantifying vacancies are mainly introduced from the aspects of microscopic characterization and spectral characterization. These techniques are helpful to understand the relationship between vacancy structure and photocatalytic properties. Subsequently, the key role of vacancy in photocatalytic process is introduced from three aspects, including absorption of light, separation and migration of charge and surface reaction. Finally, the prospects and challenges of vacancy defects in photocatalytic materials are proposed. The controllability of vacancy concentration, the synergism of composite modification and the stability of vacancy are urgent problems to be solved. This review summarizes the effective strategies of vacancy modification for photocatalysis, which can provide some theoretical reference for the relevant research.
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  Preparation of Cu₂S@SSM composite membrane and its oil-water separation performance

  Jorunal of Functional Materials. 2022, 53(11): 11023-11030. https://doi.org/10.3969/j.issn.1001-9731.2022.11.004

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  Oil-water separation materials with excellent chemical stability are urgently needed in the treatment of oily wastewater. In this work, in order to effectively separate various oil-in-water emulsions in complex environments such as acid, alkali and salt, with stainless steel mesh (SSM) as the base, copper sulfide (Cu₂S) was modified on the surface of stainless steel mesh by electrochemical deposition and solution reaction to successfully prepare Cu₂S@SSM composite membrane. The prepared Cu₂S@SSM composite membrane exhibited excellent superhydrophilic/underwater superhydrophobic properties. A series of oil-in-water emulsion, including surfactant-free and surfactant-stabilized oil-in-water emulsions, separation experiments were conducted. The permeation fluxes as high as 932 and 361 L/(m²·h) and the separation efficiency as high as 99.78% and 99.15% were obtained, respectively. Thanks to the photo-Fenton catalytic performance of Cu₂S, the degradation rate of Cu₂S@SSM composite film to methylene blue and rhodamine B is up to 99% under visible light irradiation. More importantly, the Cu₂S@SSM composite membrane shows excellent chemical stability in strong acid, strong alkali and high salt environments.
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  Research on the preparation of nanoporous CoCuP and electrocatalytic property for hydrogen evolution reaction

  Jorunal of Functional Materials. 2022, 53(11): 11031-11036. https://doi.org/10.3969/j.issn.1001-9731.2022.11.005

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  The catalysts with good performance are very important to the hydrogen production. In this paper, nanoporous CoCuP catalysts with self-supported structure were prepared by electrochemical dealloying. The nanoporous structure exhibits the larger specific surface area and provides more active sites. The introduction of Cu atoms adjust the electronic structure of Co and P and improve the catalytic performance of the catalyst. The overpotential of np-Co₇₅Cu₅P₂₀ in alkaline solution is 60.6 mV, and the Tafel slope is 33.1 mV/dec. In neutral solution, the overpotential of np-Co₇₅Cu₅P₂₀ is 132.3 mV and the Tafel slope is 127 mV/dec. The catalysts can be well used in the solutions with large pH range.
Review & Advance
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  Research progress of TMSs catalyst in hydrogen production from electrolytic water

  Jorunal of Functional Materials. 2022, 53(11): 11037-11045. https://doi.org/10.3969/j.issn.1001-9731.2022.11.006

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  As a green energy with high energy density, low molecular weight and no pollution, hydrogen energy is expected to replace traditional energy in the future. Electrolytic water hydrogen production process is simple and an important method to produce high-purity hydrogen, but the reaction kinetics in the process of water electrolysis is slow, which seriously affects the efficiency of electrolytic water hydrogen production. Transition metal sulfide(TMSs)catalysts have become the focus of research because of their low price and excellent electrocatalytic performance. This paper summarizes the latest research results and applications of TMSs catalysts. Starting from the reaction mechanism of hydrogen evolution reaction(HER)and oxygen evolution reaction(OER), Through the evaluation methods of electrochemical testing and electrode characterization, the development and problems faced by TMSs catalytic materials are discussed. It focuses on the preparation methods of TMSs catalysts and analyzes their research progress in electrocatalytic hydrolysis hydrogen production technology. It provides a new idea for further improving the hydrogen production performance of TMSs by electrolyzing water.
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  Structural design, synthesis and applications of photo-thermo-catalytic materials

  Jorunal of Functional Materials. 2022, 53(11): 11046-11056. https://doi.org/10.3969/j.issn.1001-9731.2022.11.007

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  How to make full and efficient use of solar energy is the driving force leading the development of photocatalytic materials. Photo-thermal catalysis has attracted great attention of researchers because it can use full-spectrum sunlight to stimulate the synergy between luminescence catalysis and thermal catalysis to achieve high utilization efficiency of solar energy. In this paper, the design, synthesis, performance optimization and practical application of photo-thermo-catalytic materials are reviewed. The future development trend of photo-thermo-catalytic materials is also prospected here.
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  Research progress of bismuth-rich bismuth oxyhalides using as photocatalysts

  Jorunal of Functional Materials. 2022, 53(11): 11057-11064. https://doi.org/10.3969/j.issn.1001-9731.2022.11.008

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  Photocatalytic technology is regarded as one of the most promising pathways to solve the global energy shortage and environmental crisis, and the development of efficient photocatalysts with visible light response has always been a research hotspot in the photocatalytic field. As the continuation and development of traditional photocatalyst bismuth oxyhalides (BiOX, X=Cl, Br, I), the bismuth-rich bismuth oxyhalides (Bi_xO_yX_z) shows tunable band structure which benefits to improve the photocatalytic activity. The methods of controlled synthesis of Bi_xO_yX_z were summarized, including solid phase thermal conversion method, alkaline precipitation/hydrothermal/solvothermal method, etc. The photocatalytic applications of Bi_xO_yX_z were also introduced in degrading organic pollutants, splitting water to hydrogen, reducing carbon dioxide and nitrogen fixation. Finally, the current problems and future development directions of Bi_xO_yX_z were proposed. The review will deepen the understanding of Bi_xO_yX_z and open new directions for the design and optimization bismuth-based photocatalytic materials for energy and environmental applications.
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  Research progress on catalytic materials and reaction mechanism for CWPO treatment of phenolic wastewater

  Jorunal of Functional Materials. 2022, 53(11): 11065-11074. https://doi.org/10.3969/j.issn.1001-9731.2022.11.009

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  Phenolic pollutants are one of the common organic pollutants. Phenolic wastewater treatment is difficult and highly toxic, which has serious harm to the natural environment and human health. Catalytic wet hydrogen peroxide oxidation technology (CWPO) uses H₂O₂ as oxidant and catalyst to generate ·OH strong oxidizing free radicals, which can remove refractory organic pollutants in water. This paper introduces the application of CWPO non-supported and supported catalysts in phenol wastewater. Density Functional Theory (DFT) was used to analyze the main degradation pathways of phenol and m-cresol pollutants. The degradation of phenol wastewater is through ·OH in the system to gradually change the stable structure of benzene ring to form benzoquinone intermediates, and the C—C intermediates break open to form short-chain carboxylic acids, and finally completely mineralize into CO₂ and H₂O. In the future, studies can be carried out on the preparation of stable environmental protection catalyst and analysis of actual wastewater degradation mechanism, so as to exert the application potential of CWPO in phenolic wastewater.
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  Advance on preparation and surface modification strategies of zinc stannate photocatalyst

  Jorunal of Functional Materials. 2022, 53(11): 11075-11080. https://doi.org/10.3969/j.issn.1001-9731.2022.11.010

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  The emergence of zinc stannate (Zn₂SnO₄) contributes to the environmental alleviation and the energy production to a certain degree, of which has been considered as a rising star photocatalyst mainly because of its good conductivity, high electron mobility, stable physical-chemical properties and nontoxicity. In this review, we critically discussed the structure characteristics and synthesis methods for Zn₂SnO₄ photocatalyst. The representative modification strategies for Zn₂SnO₄, including ion doping, heterojunction construction, elemental loading and morphology control, were systematically summarized. Besides, its photocatalytic applications that encompass organic pollutant degradation, hydrogen production and CO₂ conversion were brief introduced. Eventually, the prospects of Zn₂SnO₄-based photocatalytic materials were also presented. It is anticipated that this review would provide new ideas and directions for the development of high-efficiency Zn₂SnO₄-based photocatalytic systems.
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  Research progress on the application and properties of photocatalytic nanomaterials prepared by microwave method

  Jorunal of Functional Materials. 2022, 53(11): 11081-11087. https://doi.org/10.3969/j.issn.1001-9731.2022.11.011

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  As a new strategy for the synthesis of nanomaterials, the microwave method not only has the characteristics of uniform heating and fast reaction speed, but also high sensitivity and selectivity. As a result, this review briefly introduces the microwave theory and heating mechanism, and then summarizes the single photocatalytic material, doped materials with different elements. Furthermore, the microwave fabrication strategy for constructing nanocomposites as well as the effect of microwave method on the microstructure and crystallization of the catalyst is well elucidated. We provide insights on the synthesis of high-performance semiconductor photocatalysts with high efficiency and low energy consumption. Finally, this review also puts forward the challenges facing by microwave synthesis of photocatalytic materials in practical applications and prospects for future development.
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  Research progress on photocatalytic hydrogen production by molecular structure modified carbon nitride

  Jorunal of Functional Materials. 2022, 53(11): 11088-11094. https://doi.org/10.3969/j.issn.1001-9731.2022.11.012

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  Graphite carbon nitride (g-C₃N₄) has been a research hotspot in the field of hydrogen production due to its unique properties and low-cost raw materials. Nevertheless, the photocatalytic efficiency of graphite carbon nitride is usually limited by its low specific surface area, insufficient visible light utilization, the fast recombination of photo-induced electron-hole pairs and other demerits. Herein, in the review, methods of molecular modification on g-C₃N₄ were reviewed from the aspects of copolymerization, covalent bonding and surface modification with functional groups. Moreover, the review also summarized the mechanism of structure modified carbon nitride in improving photocatalytic hydrogen production activity in terms of visible light absorption, separation efficiency of electrons and holes and reactivity of active sites. The review ended with perspectives on the challenges and future prospects of molecular modification of graphite carbon nitride.
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  Research progress on photocatalytic mechanism and application of TiO₂ with the different ion doping

  Jorunal of Functional Materials. 2022, 53(11): 11096-11103. https://doi.org/10.3969/j.issn.1001-9731.2022.11.013

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  As the core material of photocatalytic technology, TiO₂ has a great potential in sewage treatment, energy and medical beauty, due to its unique structure and performance. However, the large band gap, the length of excitation wave and the easy recombination of photogenerated electrons have become one of the important bottlenecks in its application. Therefore, this paper introduces the photocatalytic principle and influencing factors of TiO₂ materials, focuses on the photocatalytic mechanism and application fields of doped TiO₂. Meanwhile, the shortcomings in the modification process of TiO₂ photocatalyst were put forward, and the future research direction is prospected.
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  Research progress on ZnSn(OH)₆ as photocatalyst

  Jorunal of Functional Materials. 2022, 53(11): 11104-11110. https://doi.org/10.3969/j.issn.1001-9731.2022.11.014

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  Zinc hydroxyl stannate (ZnSn(OH)₆) is a representative hydroxyl compound with perovskite structure, and also a transition metal stannate with multiple valence states (Sn²⁺/Sn⁴⁺). Besides, the wide band gap of ZHS, and the positions of the valence and conduction bands make it have a high redox potential, thus showing good photocatalytic activity and strong stability. In this paper, the crystal structure, preparation method and the main influencing factors of photocatalytic performance over ZnSn(OH)₆ materials were introduced. Meantime, the modification strategies and application of ZnSn(OH)₆-based photocatalysts in energy and environmental field were well exemplified.
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  Research progress on silicon carbide photocatalyst

  Jorunal of Functional Materials. 2022, 53(11): 11111-11117. https://doi.org/10.3969/j.issn.1001-9731.2022.11.015

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  The design and synthesis of photocatalytic materials and their application in environmental pollution control and resource recycling have been reported in many literatures. However, most photocatalytic materials contain transition metal ions, and the environmental risks of leaching limit the application of catalytic materials. Silicon carbide (SiC), as the representative of the third generation of semiconductor materials, has a good potential application prospect in environmental pollution prevention because of its characteristics such as no transition metal ions, high temperature and acid-alkali resistance, strong stability and so on. In recent years, some literatures have reported the synthesis, modification and application of SiC as photocatalyst in environment and resource recycling fields. However, few literatures have reviewed the application progress of SiC photocatalyst. In view of the above situation, the progress in the field of SiC photocatalysis application in recent years was reviewed in this paper, including synthesis method, doping modification and application, and the prospects of the photocatalyst system were also prospected.
Research & Development
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  Catalytic performance of copper-loaded silica microspheres in phenol oxidation

  Jorunal of Functional Materials. 2022, 53(11): 11118-11125. https://doi.org/10.3969/j.issn.1001-9731.2022.11.016

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  The discharge of wastewater containing phenol and its derivatives causes serious pollution to water resources. In order to solve the problem, SiO₂-Cu²⁺ and SiO₂-CuO catalysts were prepared by impregnation, calcination and other treatment methods, using the laboratory-made SiO₂ particles as the catalyst carrier to support the active center Cu (Ⅱ). And the prepared catalysts were applied to the CWPO of phenol. Based on the conversion of phenol after degraded in aqueous solution and the COD removal rate of the sample, the effects of reaction conditions such as reaction temperature, reaction time, oxidant concentration, catalyst concentration and initial pH value of the medium on the catalytic performance of the two catalysts were systematically studied. The experimental results show that the SiO₂-Cu²⁺ and SiO₂-CuO catalysts have excellent catalytic activity in a wide pH range, and the 100% phenol conversion rate and about 90% COD removal rate can be achieved under the conditions of phenol concentration of 1.0 g/L, catalyst concentration of 0.23 g/L, reaction temperature of 70 ℃, reaction time of 20 h, and hydrogen peroxide concentration of 5.0 g/L.
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  Preparation of modified nano-TiO₂ and photocatalytic degradation of heavy metal wastewater

  Jorunal of Functional Materials. 2022, 53(11): 11126-11130. https://doi.org/10.3969/j.issn.1001-9731.2022.11.017

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  Using butyl titanate as titanium source and cerium nitrate as modifier, modified nano-TiO₂ particles with different Ce doping contents (0%, 0.3 mol%, 0.6 mol%, 0.9 mol%) were prepared by sol-gel method. The effects of different rare earth Ce doping on the phase structure, micro morphology, spectral properties and photocatalytic properties of nano-TiO₂ particles were studied by XRD, SEM, UV-Vis, PL and photocatalytic tests. The results showed that the prepared nano-TiO₂ particles were anatase phase with high crystallinity. After adding rare earth Ce, the morphology of nano-TiO₂ particles gradually became regular spherical, and the grains were refined. When the doping amount of rare earth Ce was 0.6 mol%, the grain size of TiO₂ particles was the most regular and the distribution was the most uniform. The absorption sideband of rare earth Ce doped nano-TiO₂ particles had a red shift and the absorption sideband increased, and the doping of rare earth Ce effectively inhibited the recombination of electron hole pairs. The degradation efficiency of Cr(Ⅵ) in heavy metal wastewater had been significantly improved by rare earth Ce modified nano-TiO₂ particles, and when the doping amount of rare earth Ce was 0.6 mol%, the highest degradation efficiency of nano-TiO₂ at 180 min was 92.7%, which was 166.4% higher than that of pure nano-TiO₂. Comprehensive analysis showed that the optimum doping ratio of rare earth Ce was 0.6 mol%.
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  Influence from N doing and surface functional groups of graphene on the photocatalytic performance of TiO₂

  Jorunal of Functional Materials. 2022, 53(11): 11131-11135. https://doi.org/10.3969/j.issn.1001-9731.2022.11.018

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  Composite photocatalysts were prepared by the hydrothermal method with graphene and TiO₂ as start materials. The total amount of surface functional groups and doping density of N atom of graphene were adjusted to reveal the potential influence on the photocatalytic actives of the as-prepared samples. The doping N atoms improved the photocatalytic performance, while the presence of surface functional groups promoted the formation of π-d coupling between the graphene basal plane and TiO₂ nanoparticles. The rate constant of the optimized specimens was 5.82×10^-2 /min under the UV-light irradiation, which was 1.47 times higher than that of the pure TiO₂. On the other hand, the rate constant increased to 2.49×10^-2 /min (the cutoff of incident light is 510 nm).
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  Bifunctional Fe-doped MoS₂ nanosheets as efficient electrocatalysts for water splitting

  Jorunal of Functional Materials. 2022, 53(11): 11136-11142. https://doi.org/10.3969/j.issn.1001-9731.2022.11.019

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  The design and synthesis of non-noble metal electrolytic hydropower catalysts with high activity and durability are of great significance for energy conversion and storage. In this study, iron doped molybdenum disulfide nanomaterials were prepared by a simple hydrothermal reaction of ferric nitrate, thioacetamide and sodium molybdate in anhydrous ethanol. It showed high oxygen evolution reaction (OER) activity. In 1 M KOH electrolyte, when the current density was 10 mA/cm², the overpotential was 250 mV, the Tafel slope was 219 mV/dec, and the Fe-MoS₂ could be stabilized for more than 10 h. The hydrogen evolution reaction (HER) activity was 220 mV when the current density reached 10 mA/cm² in 0.5 M H₂SO₄ electrolyte. In addition, in 1.0 M KOH electrolyte, Fe-MoS₂/C (anode) ∥Fe-MoS₂/C (cathode) two-electrode system has good catalytic activity for total hydrolysis with a low potential of 1.77 V at a current density of 10 mA/cm². Therefore, this study presents an effective technical support for the development of transition metal-doped transition metal sulfides with efficient electrolytic water performance.
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  Preparation of nanoporous MoNi/Al₃Ni₂ structure and study on electrocatalytic properties for hydrogen evolution

  Jorunal of Functional Materials. 2022, 53(11): 11143-11149. https://doi.org/10.3969/j.issn.1001-9731.2022.11.020

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  The development of non-precious metal high-efficiency electrocatalysts is the key to reducing the cost of hydrogen production from water electrolysis. In this paper, a self-supporting nanoporous MoNi/Al₃Ni₂ catalyst was prepared on a nickel foam substrate by laser direct writing and dealloying. The nanoporous structure of the catalyst produces more active sites after dealloying, and the synergistic effect between MoNi and Al₃Ni₂ enables the catalyst to exhibit excellent HER performance in alkaline medium (1 mol/L KOH). The MoNi/Al₃Ni₂ catalyst with Al content of 80% shows an overpotential of only 31 mV at a current density of 10 mA/cm² along with impressive stability at the current density of 10 mA/cm² for 100 h, which provides a good strategy for hydrogen evolution in industrial water splitting.
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  Biosynthesis and photocatalytic performance of ferric oxide nanocatalysts

  Jorunal of Functional Materials. 2022, 53(11): 11150-11157. https://doi.org/10.3969/j.issn.1001-9731.2022.11.021

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  Biosynthesis of iron oxide nanoparticles (Fe₂O₃ NPs) by Pseudomonas Aeruginosa and Bacillus Velezensis has been studied. The effects of preparation conditions on the synthesis of Fe₂O₃ NPs by Pseudomonas Aeruginosa and Bacillus Velezensis were studied. The process variables of preparation Fe₂O₃ NPs were optimized, the XRD, BET, TEM, FT-IR and other characterization of Fe₂O₃ NPs were carried out to explore the catalytic degradation by visible light. Using methyl violet and isothiazolinone as organic pollutant models, their photocatalytic performance was explored. After 5 h of blue light irradiation, with the amount of catalyst 0.03 g and the initial concentration of methyl violet solution 10 mg/L, the degradation rates of methyl violet by Fe₂O₃@PA (prepared by Pseudomonas Aeruginosa) and Fe₂O₃@BV (prepared by Bacillus Velezensis) reached 61.29% and 69.87%, respectively. When the amount of catalyst was 0.03 g, the initial concentration of isothiazolinone solution was 30 mg/L and the pH was 5, after 4.5 h UV irradiation at pH 5, the degradation rates of Fe₂O₃@PA and Fe₂O₃@BV to isothiazolinone reached 76.21% and 82.13%, respectively.
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  Preparation of Ag-ZnO nanomaterials and their performance in catalytic reduction of 4-NP

  Jorunal of Functional Materials. 2022, 53(11): 11158-11162. https://doi.org/10.3969/j.issn.1001-9731.2022.11.022

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  Ag-ZnO nanomaterials were synthesized by a simple hydrothermal method, and the nanomaterials were characterized by SEM, EDS, XRD and XPS. This were used as catalysts for p-nitrophenol (4-NP) reduction reaction. The results show that Ag-ZnO nanomaterials can catalyze the reduction of 4-NP to p-aminophenol (4-AP) within 8 min, with a catalytic efficiency of up to 99.5%. The catalytic efficiency remains at about 90% in the fifth cycle of the reaction. The Ag-ZnO nanomaterials have high catalytic activity and long cycle life.
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  Preparation of P doped BiOBr photocatalyst and its nitrogen fixation performance

  Jorunal of Functional Materials. 2022, 53(11): 11163-11169. https://doi.org/10.3969/j.issn.1001-9731.2022.11.023

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  BiOBr have received extensive interest for photocatalytic nitrogen fixation due to their special layered structure. In this paper, a series of P-doped BiOBr photocatalysts were successfully synthesized using sodium hypophosphite and bismuth nitrate pentahydrate as precursors through solvothermal process. The XRD, SEM, XPS, UV-Vis DRS, and photocatalytic materials were used to characterize the as-prepared catalyst. The photocatalytic nitrogen fixation performance under visible light irradiation was investigated. The results showed that P-doping increased the specific surface area of BiOBr and did not change its crystal structure. At the same time, P-doping improved the separation efficiency and visible light response of photogenerated carriers. Compared with BiOBr, the photocatalytic ammonia production of P-doped BiOBr (n(Bi):n(P) =15: 1) was 31.68 mg/(L·h·g)_cat, which was 4.7 times higher than that of BiOBr. Finally, the P-doped BiOBr has good stability after four cycles of experiments.
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  Synthesis of Ag/3D-reduced graphene oxide nanocomposite and its catalytic performance

  Jorunal of Functional Materials. 2022, 53(11): 11170-11176. https://doi.org/10.3969/j.issn.1001-9731.2022.11.024

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  To conquer the easy agglomeration of silver nanoparticles, 3D reduced graphene oxide was chosen as support for silver nanoparticles, and the Ag/3D-reduced graphene oxide (Ag/3D-rGO) nanocomposite was synthesized via one-pot green hydrothermal method. The morphology and structure of Ag/3D-rGO were characterized by SEM, XRD, FTIR, Raman, and XPS in detail. The catalytic performance of the as-synthesized nanocomposite was tested with the catalytic reduction of 4-nitrophenol (4-NP) at room temperature as model. The results show the Ag/3D-rGO nanocomposite was synthesized successfully. The nanocomposite showed well-defined and continuous inter-connected 3D porous network. The silver nanoparticles were decorated on the surface of the pore wall homogeneously, and no obvious agglomeration could be detected. With the Ag/3D-rGO nanocomposite as catalyst, the catalytic reduction of 4-NP can be completed within 2 min. The above reaction followed the first-order catalytic kinetic reaction law, and the corresponding first-order catalytic kinetic constant was determined to be 1.8694 /min, which was much higher than similar materials in reported literatures. The reported method was green and simple, and the obtained nanocomposite with excellent catalytic performance held broad application prospects in industrial catalysis and environmental protection.
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  Preparation of Al₂O₃ ceramics with pittosporum leaves as template and their adsorption-photocatalytic properties

  Jorunal of Functional Materials. 2022, 53(11): 11177-11183. https://doi.org/10.3969/j.issn.1001-9731.2022.11.025

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  Taking the common leaves of Pittosporum as a biological template, and using the unique morphological structure of the leaves, Al₂O₃ with a hierarchical porous structure was prepared by means of pretreatment, impregnation, drying and roasting. XRD, SEM, N₂ physical adsorption, etc. means were conducted to characterize materials. Methylene blue (MB, C₁₆ H₁₈ClN₃S·3H₂O) was used as a simulated pollutant to explore the adsorption and photocatalytic properties of the material. The results show that the leaf skeleton of P. chinensis is covered with Al₂O₃, which perfectly restores the stomatal structure inside and on the surface of the leaves. The specific surface area is as high as 28.3 m²/g, and the adsorption rate of methylene blue is 29.4%, showing good adsorption performance and photocatalytic performance.
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  The study of Ce³⁺-doped ZnO on photocatalytic properties

  Jorunal of Functional Materials. 2022, 53(11): 11184-11191. https://doi.org/10.3969/j.issn.1001-9731.2022.11.026

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  In this study, Ce³⁺-doped ZnO nanomaterials with different concentrations were prepared by hydrothermal method. The prepared samples were characterized by X-ray diffractometer (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), energy dispersive spectrometer (EDS), photoluminescence (PL), and Brunauer Emmett Teller (BET). Among them, XRD confirmed the successful doping of Ce³⁺, PL showed that Ce³⁺-doped inhibited the recombination of electron-hole pairs, and BET found that Ce³⁺-doped increased the specific surface area of ZnO. Photodegradation experiments were performed on aqueous solutions of Rhodamine B (RhB) under simulated daylight conditions. The experiments results showed that the photocatalytic performance of all Ce³⁺-doped samples was better than that of undoped ZnO. It was found that the sample (.1% Ce³⁺ doped ZnO) exhibited the best photocatalytic performance (degradation efficiency of 95.6%). The photocatalytic mechanism of Ce³⁺-doped ZnO was also presented.
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  Photocatalytic performance of semiconductors with ferroelectric polarization-generated built-in electric field

  Jorunal of Functional Materials. 2022, 53(11): 11192-11197. https://doi.org/10.3969/j.issn.1001-9731.2022.11.027

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  Spontaneous polarization of ferroelectric materials can generate a built-in electric field. In this study, Ag₂O and CdS nanoparticles were supported on ferroelectric LiNbO₃ and glass substrates by physical dispersion method, and Rhodamine B (RhB) was selected as a representative organic pollutant to evaluate the photocatalytic degradation efficiency of Ag₂O and CdS on the different substrates. The results show that the photocatalytic activity of the same semiconductor nanoparticles on different substrates is LiNbO₃(+Z) > glass > LiNbO₃(-Z). On the same substrate, Ag₂O exhibits better photocatalytic activity than CdS. Based on the polarization-generated built-in electric field at the interface of semiconductor/ferroelectric and the photocatalytic degradation reaction, the mechanism of ferroelectric polarization affecting the photocatalytic degradation performance of semiconductors is proposed.
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  Construction and photocatalytic properties of graphene/g-C₃N₄ composite photocatalyst

  Jorunal of Functional Materials. 2022, 53(11): 11198-11205. https://doi.org/10.3969/j.issn.1001-9731.2022.11.028

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  In this experiment, graphite phase carbon nitride (g-C₃N₄) has been use as a photocatalyst to study the problems of small specific surface area and low visible light efficiency. Firstly, the graphene oxide (GO) and reduced graphene oxide (rGO) were respectively synthesized with g-C₃N₄ in a certain proportion by ultrasonic assisted synthesis method. And the composites were characterized and analyzed by XRD, SEM, FT-IR, XPS, UV-Vis and other characterization methods. Secondly, the photocatalytic degradation and kinetics of rhodamine B (RhB) under simulated sunlight were studied. Finally, the experimental results show that the GO/CN and rGO/CN composite photocatalysts have the same phase structure and more porous morphology as g-C₃N₄, and the graphene composite material can improve the visible light absorption capacity of g-C₃N₄, and reduce its band gap width. Also, according to the analysis of visible light photocatalytic performance, rGO/CN2 has stronger adsorption capacity, and the adsorption rate f RhB at 30 min is up to 64.79%, 5.2 times that of g-C₃N₄ under the same conditions. GO/CN1.5 shows excellent photocatalytic activity, and its catalytic reaction rate constant is 9.108×10^-2/min. When RhB is degraded for 10 min, the degradation rate reaches 86.34%, which is 1.5 times that of g-C₃N₄ under the same conditions.
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  Preparation and photocatalytic properties of nano-TiO₂-Pt composites under visible light

  Jorunal of Functional Materials. 2022, 53(11): 11206-11211. https://doi.org/10.3969/j.issn.1001-9731.2022.11.029

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  Nano-rod-like anatase TiO₂ sol was prepared by low temperature hydrothermal method, and nano-Tio₂-Pt composites with different contents of Pt were prepared by noble metal deposition using chloroplatinic acid as Pt source. The surface morphology and optical properties of nano-Tio₂-Pt composites were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV-vis absorption spectroscopy and X-ray photoelectron spectroscopy. The photocatalytic degradation of methylene blue (MB) aqueous solution was carried out using xenon lamp to simulate visible light source, and the photocatalytic activity of the sample was evaluated by the degradation efficiency. The results show that the size of titanium dioxide sol prepared was standard anatase type with uniform size. Moreover, Pt nanoparticles were well dispersed on the surface of TiO₂. Because of the existence of platinum layer, photoelectron-hole recombination was inhibited, the life of photocarrier was prolonged, and the quantum efficiency was improved. The photocatalytic activity of Tio₂-Pt was much higher than that of TiO₂, and the degradation efficiency of methylene blue reached 88.5%.
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  Preparation of g-C₃N₄ /Cu-TiO₂ nanospheres and characterization of catalytic properties in UV-assisted fenton

  Jorunal of Functional Materials. 2022, 53(11): 11212-11219. https://doi.org/10.3969/j.issn.1001-9731.2022.11.030

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  g-C₃N₄/Cu-TiO₂ nanospheres with excellent photocatalytic performance were prepared by hydrothermal method based on 7% wt Cu-TiO₂ prepared by one-step method. The structure, morphology and optics of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV-visible diffuse reflectance spectroscopy (UVVis DRS). Rhoda mine B was used as a simulated pollutant to characterize its photocatalytic performance under UV light. The results showed that the synthesized catalysts were 80-90 nm smooth nanospheres uniformly distributed on the lamellar g-C₃N₄, and the degradation rate of 25 mg/L Rhoda mine B reached 92.71% within 20 min in the UV Fenton system (0.1 mL 30% H₂O₂) with 60% wt g-C₃N₄/Cu-TiO₂. It reached 100% in 30 min. At the same time, it has the same efficient catalytic effect in the pH range of 2~8, which significantly improves the catalytic efficiency and the applicable pH range.
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  Structure and catalytic properties of Ag-doped ZnO nanorods prepared by solvothermal method

  Jorunal of Functional Materials. 2022, 53(11): 11220-11224. https://doi.org/10.3969/j.issn.1001-9731.2022.11.031

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  In order to improve the photodegradation efficiency of ZnO, the noble metal Ag is selected as the doping material. ZnO nanorods with different Ag doping amounts (0, 1 mol%, 2 mol%, 3 mol% and 4 mol%) were prepared by solvothermal method. The lattice structure, micro morphology, spectral properties and catalytic properties of ZnO were characterized by XRD, SEM, FT-IR and PL, and the degradation efficiency of Rhodamine B by Ag-doped ZnO nanorods under 500 W xenon lamp irradiation was studied. The results showed that the crystal structure of Ag-doped ZnO didn’t change, but the cell volume increased and the lattice distortion decreased. After Ag doping, ZnO gradually changed from spherical particle to rod structure, and the change trend was more obvious with the increase of Ag doping ratio. Part of Ag ⁺ replaced Zn²⁺, resulting in the decrease of the vibration peak of metal oxygen bond of Ag-doped ZnO. With the increase of Ag doping concentration, the PL intensity of ZnO nanorods decreased first and then increased, and the PL intensity of 3 mol% Ag-doped ZnO was the lowest. Ag doping inhibited the electron hole recombination and enhanced the photodegradation efficiency. The degradation efficiency of Rhodamine B by 3 mol% Ag-doped ZnO nanorods reached the maximum of 70.22% under 120 min irradiation.
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  Preparation of ruthenium-based catalyst and its electrocatalytic performance for hydrogen evolution

  Jorunal of Functional Materials. 2022, 53(11): 11225-11230. https://doi.org/10.3969/j.issn.1001-9731.2022.11.032

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  Electrochemical decomposition of water producing hydrogen is a pollution-free method with great prospects. The design of less money catalysts with high efficiency catalytic properties is very important for the large-scale application of easing environmental pressure and electrocatalytic hydrogenation. With the pineal shell (PC) as the precursor of biomass carbon, the urea as the source of nitrogen, and RuCl₃ as the source of ruthenium supply, Ru was fixed on the carbon matrix derived from nitrogen-doped biomass (Ru-N-CPC) through hydrothermal and high temperature carbonization method. The manufactured Ru-N-CPC has good electrochemical properties, whose overpotential of 61 mV can reach a current density of 10 mA/cm², as well as the stability. A battery of tests show that the good hydrogen evolution performance of the catalyst can be attributed to most defects caused by nitride doping, which can seal Ru smoothly and evenly into carbon materials. At the same time, due to the synergy between Ru and N, the catalyst activity has also improved a lot.
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  Preparation and characterization of RGO- TiO₂ nanocomposites for photodegradation of phenol

  Jorunal of Functional Materials. 2022, 53(11): 11231-11236. https://doi.org/10.3969/j.issn.1001-9731.2022.11.033

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  Graphene oxide was prepared by improved Hummers method. RGO-TiO₂ nanocomposites were prepared by sol-gel process combined with heat treatment process. The effects of crystal structure, micro morphology and RGO doping on the catalytic properties of the composites were studied. The results showed that RGO-TiO₂ nanocomposites were standard anatase, and nano-TiO₂ particles were evenly distributed on the surface of lamellar grapheme and good combination. Infrared analysis showed that graphene and TiO₂ in 3%RGO-TiO₂ nanocomposites formed stable Ti-O-C bond in the form of chemical combination. With the increase of RGO doping, the removal of phenol by RGO-TiO₂ nanocomposites increased first and then decreased, and the highest removal rate of 3%RGO-TiO₂ nanocomposites was 93.9% at 12 h. The removal rate of phenol reached 96.1% at 12 h under the acidic condition of pH=3, which was significantly higher than that in neutral and alkaline environment.