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Facile Synthesis of Silver-Doped Copper Selenide Composite for Enhanced Electrochemical Detection of Ecological Toxic Nitrobenzene 银掺杂硒化铜复合材料的快速合成及其对生态毒性硝基苯的电化学检测
IF 3.1 4区 化学 Q2 Chemistry Pub Date : 2023-01-06 DOI: 10.1007/s12678-022-00803-w
Arjunan Karthi Keyan, Dhanapal Vasu, Subramanian Sakthinathan, Te-Wei Chiu, Yi-Hsuan Lee, Chia-Cheng Lin

Nitrobenzene(NB) is frequently utilized in the production of numerous products and aromatic compounds. Highly toxic nitrobenzene (NB) and its derivatives mix with water resources and cause various serious effects on human health and the environmental ecosystem. It is vital to accurately detect highly dangerous aromatic nitro compounds in the water medium for the sake of safeguarding both human health and environmental safety. Hence, the detection of NB and its derivatives is one focus of electrochemical sensor development. In this work, a sensitive NB sensor has been developed using Ag-CuSe composite. The prepared Ag-CuSe composite modified with a glassy carbon electrode (GCE) has been used for the detection of NB and real sample analysis. In addition, the morphology, crystallinity, and functionality of the Ag-CuSe composite have been determined by X-ray diffraction, field emission scanning electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and elemental mapping. The electrocatalytic reduction mechanism and kinetic parameters of the NB at the GCE/Ag-CuSe electrode have been evaluated by cyclic voltammetry, differential pulse voltammetry, and amperometry in 0.05 M phosphate buffer solution (pH 7.0). The GCE/Ag-CuSe-modified electrode exhibited excellent electrochemical activity toward the detection of NB with a low limit of detection (S/N = 3) of 0.01 µM, good sensitivity of 3.64 µA µM−1 cm−2, and a linear response range of 0.1 to 400 µM. Moreover, the Ag-CuSe-modified electrode has excellent selectivity, repeatability, reproducibility, and anti-interference ability, as well as good stability. The prepared GCE/Ag-CuSe electrode has been successfully applied to the removal of pollutants from various real water samples with good recovery results. The proposed GCE/Ag-CuSe electrode has been used for the trace-level detection of nitrobenzene in environmental samples.

硝基苯(NB)经常用于许多产品和芳香族化合物的生产。剧毒的硝基苯及其衍生物与水资源混合,对人类健康和环境生态系统造成各种严重影响。准确检测水介质中高度危险的芳香族硝基化合物对保障人体健康和环境安全至关重要。因此,铌及其衍生物的检测是电化学传感器发展的热点之一。在这项工作中,利用Ag-CuSe复合材料开发了一种灵敏的NB传感器。制备的Ag-CuSe复合材料经玻碳电极(GCE)修饰后,用于NB的检测和实际样品的分析。此外,通过x射线衍射、场发射扫描电子显微镜、高分辨率透射电子显微镜、x射线光电子能谱和元素映射确定了Ag-CuSe复合材料的形貌、结晶度和功能。采用循环伏安法、差分脉冲伏安法和安培法在0.05 M磷酸盐缓冲溶液(pH 7.0)中考察了NB在GCE/Ag-CuSe电极上的电催化还原机理和动力学参数。GCE/ ag - cuse修饰电极对NB的检测具有良好的电化学活性,低检测限(S/N = 3)为0.01µM,灵敏度为3.64µaµM−1 cm−2,线性响应范围为0.1 ~ 400µM。此外,ag - cu修饰电极具有优良的选择性、重复性、再现性、抗干扰能力和良好的稳定性。制备的GCE/Ag-CuSe电极已成功应用于各种实际水样中污染物的去除,回收效果良好。本文提出的GCE/Ag-CuSe电极已用于环境样品中痕量硝基苯的检测。
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引用次数: 2
Development of Unsupported Ru and Ni Based Oxides with Enhanced Performance for the Oxygen Evolution Reaction in Acidic Media 在酸性介质中增强析氧性能的无负载Ru和Ni基氧化物的研制
IF 3.1 4区 化学 Q2 Chemistry Pub Date : 2023-01-02 DOI: 10.1007/s12678-022-00798-4
Franschke A. Soudens, Simoné Karels, Cecil Felix, Sivakumar Pasupathi

The high cost of catalyst materials suitable for the oxygen evolution reaction (OER) in polymer electrolyte membrane water electrolyzers (PEMWE) is still a major hurdle that needs overcoming before commercial PEMWE can have a meaningful impact as a technology in the hydrogen economy. Metal oxides based on precious metals are currently still the most reliable and most used materials as catalysts in PEMWE; however, alternative or modified materials are desirable to help reduce the cost associated with the catalyst component. In this study, we report on binary metal oxide catalysts based on Ru and Ni. Ni-based electrodes are typically used in alkaline water electrolyzers due to their high performance, robustness and low cost; however, Ni and NiO electrodes do not show promising performance in acidic environments due to corrosion. By combining NiO with acid stable RuO2, we have demonstrated that the performance of the RuO2 catalyst can be improved and due to the lower cost of Ni, the cost of the catalyst can ultimately be reduced. The Ni addition was limited to 10 mol% to achieve improved OER performance followed by noticeable performance degradation as the Ni composition was increased. The metal oxide catalysts were synthesized via a modified Adams fusion method that produced nano-sized catalysts with superior performance compared to a state-of-art commercial RuO2 catalyst. Physical characterizations were performed via high-resolution transmission electron microscopy, X-ray diffraction, energy dispersive X-ray, and Brunauer Emmett Teller analyses. OER performances were evaluated via cyclic voltammetry, linear sweep voltammetry, chronopotentiometry, and chronoamperometry analyses.

Graphical Abstract

聚合物电解质膜式水电解槽(PEMWE)中适合析氧反应(OER)的催化剂材料的高成本仍然是商业化PEMWE技术在氢经济中产生有意义的影响之前需要克服的主要障碍。基于贵金属的金属氧化物目前仍然是PEMWE中最可靠和最常用的催化剂材料;然而,替代或改性材料是可取的,以帮助降低与催化剂组分相关的成本。在这项研究中,我们报道了基于Ru和Ni的二元金属氧化物催化剂。镍基电极因其高性能,坚固性和低成本而通常用于碱性水电解槽;然而,由于腐蚀,Ni和NiO电极在酸性环境中表现出良好的性能。通过将NiO与酸稳定的RuO2结合,我们证明了RuO2催化剂的性能可以得到改善,并且由于Ni的成本较低,最终可以降低催化剂的成本。Ni添加量限制在10 mol%,以提高OER性能,但随着Ni成分的增加,性能明显下降。金属氧化物催化剂是通过改进的Adams融合方法合成的,与最先进的商用RuO2催化剂相比,该方法生产的纳米级催化剂具有优越的性能。通过高分辨率透射电子显微镜、x射线衍射、能量色散x射线和布鲁诺尔埃米特泰勒分析进行物理表征。通过循环伏安法、线性扫描伏安法、时间电位法和时间电流法分析来评估OER性能。图形抽象
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引用次数: 2
Electrochemical Deposited Amorphous Bimetallic Nickle-Iron (Oxy)hydroxides Electrocatalysts for Highly Efficient Oxygen Evolution Reaction 电化学沉积非晶双金属镍铁(氧)氢氧化物的高效析氧反应电催化剂
IF 3.1 4区 化学 Q2 Chemistry Pub Date : 2022-12-31 DOI: 10.1007/s12678-022-00808-5
Zhichao Xu, Jianmin Wang, Jiajia Cai, Yitao He, Jing Hu, Haijin Li, Yongtao Li, Yong Zhou

The low-cost and high-performance electrocatalysts, especially metal (oxy)hydroxides, for the oxygen evolution reaction (OER) have attracted considerable attention due to their promising OER activity. Amorphous electrocatalysts are often superior to their crystalline counterparts due to their more actives and structural flexibility. However, using traditional preparation techniques still presents a significant barrier. Herein, the amorphous NiFe (oxy)hydroxides on nickel foam (NF) with large surface area and small charge transfer resistance were fabricated by electrodeposition technique. The as-fabricated NiFe (oxy)hydroxides (Ni:Fe = 1:3) exhibited remarkable electrocatalytic activity and stability for OER with a low overpotential of 245 mV at a current density of 100 mA cm–2, a small Tafel slope of 76.9 mV dec−1, which was superior to that of noble metal electrocatalysts (RuO2) and most NiFe-based electrocatalysts. This work provides a facile and effective way to synthesis metal (oxy)hydroxide catalysts towards high-efficiency water splitting.

低成本、高性能的析氧反应电催化剂,特别是金属(氧)氢氧化物因其良好的析氧活性而受到广泛关注。无定形电催化剂由于具有更强的活性和结构灵活性而优于晶体电催化剂。然而,使用传统的制备技术仍然存在很大的障碍。采用电沉积技术在泡沫镍表面制备了具有大表面积和小电荷转移电阻的非晶态NiFe(氧)氢氧化物。制备的NiFe(氧)氢氧化物(Ni:Fe = 1:3)对OER具有良好的电催化活性和稳定性,电流密度为100 mA cm-2,过电位为245 mV, Tafel斜率较小,为76.9 mV dec−1,优于贵金属电催化剂(RuO2)和大多数NiFe基电催化剂。本研究为制备高效水裂解金属(氧)氢氧化物催化剂提供了一种简便有效的方法。
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引用次数: 1
Gamma Radiolysis-Synthesized Carbon Nanotube–Supported Palladium as Electrocatalyst for Oxygen Reduction Reaction γ射线裂解-合成碳纳米管负载钯作为氧还原反应的电催化剂
IF 3.1 4区 化学 Q2 Chemistry Pub Date : 2022-12-26 DOI: 10.1007/s12678-022-00807-6
Thye-Foo Choo, Nurazila Mat Zali, Nur Ubaidah Saidin, Kuan-Ying Kok

Electrocatalysts are used to promote efficient energy conversion in fuel cell, especially for the sluggish oxygen reduction reaction (ORR) at the cathode that inhibits the performance of the device. In this work, we demonstrate the use of a facile gamma radiolysis technique to synthesize carbon nanotube-supported palladium (Pd) metal particles as electrocatalysts for the ORR application. The Pd precursor concentration used in the preparation process was found to contribute greater effects on the Pd content and Pd crystallite size of the synthesized product compared to the gamma irradiation dose. The results showed that gamma radiolysis could successfully reduce Pd ions from its precursor solution as evidenced from field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD) characterization. The optimal ORR electrocatalyst was prepared using 0.01-M Pd precursor and a gamma radiation dose of 50 kGy. It displays a high half-wave potential (E1/2) of 0.84 V (vs. RHE) and superior electron transfer number (n) of 3.96, as well as a low peroxide yield of 1.8%. This impressive ORR electrocatalytic performance was also attributed to the synergistic effect of Pd metal particles with CNT. The findings showed that Pd/CNT is a promising electrocatalyst for ORR application and that gamma radiolysis provides a facile and eco-friendly approach in synthesizing electrocatalysts.

电催化剂被用于提高燃料电池的能量转换效率,特别是在阴极上缓慢的氧还原反应(ORR)抑制了设备的性能。在这项工作中,我们展示了使用一种简单的伽马辐射分解技术来合成碳纳米管负载的钯(Pd)金属颗粒作为ORR应用的电催化剂。与γ辐照剂量相比,制备过程中使用的Pd前驱体浓度对合成产物的Pd含量和Pd晶粒尺寸的影响更大。结果表明,从场发射扫描电镜(FESEM)、能量色散x射线能谱(EDS)和x射线衍射(XRD)表征中可以看出,γ射线裂解可以成功地从前驱体溶液中还原Pd离子。以0.01 m Pd为前驱体,γ辐射剂量为50 kGy,制备了最佳的ORR电催化剂。它具有0.84 V(相对于RHE)的高半波电位(E1/2)和3.96的优越电子转移数(n),以及1.8%的低过氧化物收率。这种令人印象深刻的ORR电催化性能也归功于钯金属颗粒与碳纳米管的协同效应。研究结果表明,Pd/CNT是一种很有前途的ORR电催化剂,而伽马射线裂解为电催化剂的合成提供了一种简便、环保的方法。
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引用次数: 1
Simultaneous Detection of Dopamine and Paracetamol on Electroreduced Graphene Oxide–Cobalt Phthalocyanine Polymer Nanocomposite Electrode 电还原氧化石墨烯-酞菁钴聚合物纳米复合电极上多巴胺和扑热息痛的同时检测
IF 3.1 4区 化学 Q2 Chemistry Pub Date : 2022-12-24 DOI: 10.1007/s12678-022-00806-7
Charles Luhana, Philani Mashazi

Abstract

The fabrication of sensitive, fast, cost-effective and eco-friendly electrochemical sensors is essential for monitoring analytes of biomedical, environmental and pharmaceutical interests. Herein, we report the simultaneous electroreduction and deposition of graphene oxide (GO) to form electrochemically reduced graphene oxide (ERGO) onto a glassy carbon electrode (GCE) represented as GCE-ERGO. Onto the GCE-ERGO, cobalt (II) tetra-amino phthalocyanine was electropolymerized to form a stable GCE-ERGO/polyCoTAPc. The sensing surface, GCE-ERGO/polyCoTAPc, was characterized using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques to ascertain its electron transfer and conducting properties. The modifier surface functional groups and composition were confirmed using infrared spectroscopy and energy-dispersive X-ray spectroscopy. The prepared sensing electrode displayed enhanced electrocatalytic activity towards ferri/ferrocyanide {[Fe(CN)6]3−/4−} as a redox probe. GCE-ERGO/polyCoTAPc was further used for ultrasensitive simultaneous detection and determination of dopamine (DA) and paracetamol (PA). The electrocatalytic peak currents for DA and PA were greatly enhanced with an oxidation potential difference of 264 mV, wide enough for simultaneous determination. Using differential pulse voltammetry (DPV), the electrocatalytic oxidation peak currents of DA and PA at GCE-ERGO/polyCoTAPc showed linear dependence with the changes in concentrations up to 100 µM for DA and up to 90 µM for PA. The limits of detection (LOD) values were 0.095 µM and 0.10 µM using a signal-to-noise (S/N) ratio of 3 for DA and PA, respectively. The GCE-ERGO/polyCoTAPc displayed excellent sensitivity of 8.39 µA µM−1 cm−2 for DA and 1.32 µA µM−1 cm−2 for PA. The fabricated ultrasensitive electrochemical sensor was successfully used for the determination of DA and PA in synthetic urine samples with excellent percentage recoveries.

摘要制备灵敏、快速、经济、环保的电化学传感器对于生物医学、环境和制药领域的分析物监测至关重要。在此,我们报道了氧化石墨烯(GO)的同时电还原和沉积,以形成电化学还原的氧化石墨烯(ERGO)到玻璃碳电极(GCE)上,表示为GCE-ERGO。在GCE-ERGO上,钴(II)四氨基酞菁电聚合形成稳定的GCE-ERGO/polyCoTAPc。利用循环伏安法(CV)和电化学阻抗谱(EIS)技术对传感表面GCE-ERGO/polyCoTAPc进行了表征,以确定其电子转移和导电性能。利用红外光谱和能量色散x射线光谱确定了改性剂的表面官能团和组成。所制备的传感电极对铁/亚铁氰化物{[Fe(CN)6]3−/4−}作为氧化还原探针表现出增强的电催化活性。进一步采用GCE-ERGO/polyCoTAPc超灵敏同时检测和测定多巴胺(DA)和扑热息痛(PA)。DA和PA的电催化峰电流明显增强,氧化电位差为264 mV,足以同时测定。采用差分脉冲伏安法(DPV),在GCE-ERGO/polyCoTAPc上,DA和PA的电催化氧化峰电流随DA浓度≥100µM和PA浓度≥90µM的变化呈线性关系。DA和PA的检出限(LOD)分别为0.095µM和0.10µM,信噪比为3。GCE-ERGO/polyCoTAPc对DA的灵敏度为8.39µAµM−1 cm−2,对PA的灵敏度为1.32µAµM−1 cm−2。所制备的超灵敏电化学传感器成功地用于合成尿液样品中DA和PA的测定,并具有良好的回收率。
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引用次数: 6
Electrochemical Detection of Nevirapine Using Banana Peel Extract Functionalised Nickel Selenide Quantum Dots 香蕉皮提取物功能化硒化镍量子点电化学检测奈韦拉平
IF 3.1 4区 化学 Q2 Chemistry Pub Date : 2022-12-24 DOI: 10.1007/s12678-022-00805-8
Ginny S. Tito, Alex T. Kuvarega, Bhekie B. Mamba, Usisipho Feleni

Nickel selenide quantum dots (NiSe2QDs) were synthesised using the aqueous colloidal method with banana peel extract (BPE) utilised as a capping agent. A gold electrode modified with the BPE-capped NiSe2QDs was used for the determination of nevirapine. Characterisation of the BPE-NiSe2QDs was conducted using high-resolution scanning electron microscopy (HRSEM), high-resolution transmission microscopy (HRTEM) and small-angle X-ray scattering (SAXS) which all revealed the spherical morphology of the QDs and their small sizes (˂ 10 nm). Optical properties of the BPE-NiSe2QDs studied by ultraviolet–visible spectroscopy (UV–Vis) revealed an absorbance band at 329 nm corresponding to an energy bandgap value of 2.99 eV. The electrochemical experiments were performed using differential pulse voltammetry. The Au/BPE-NiSe2QDs/Nafion-based electrochemical sensor showed a distinctive anodic response towards nevirapine at 0.76 V. The results obtained showed that the oxidation peak current increased linearly as the nevirapine concentrations increased in the range 0–1.21 pM (0–0.322 ng/L) with a low limit of detection (LOD) of 0.024 pM (0.0064 ng/L) and sensitivity of 5.52 µA/pM. These exceptional properties are comparable to or even better than already reported sensors for complex matrices. The electrochemical sensor demonstrated high repeatability and stability. The proposed sensor was successfully used for nevirapine detection in spiked wastewater samples with satisfactory results.

以香蕉皮提取物(BPE)为封盖剂,采用水溶胶法制备硒化镍量子点(NiSe2QDs)。用bpe包封的NiSe2QDs修饰金电极测定奈韦拉平。利用高分辨率扫描电镜(HRSEM)、高分辨率透射电镜(HRTEM)和小角度x射线散射(SAXS)对BPE-NiSe2QDs进行了表征,结果表明,BPE-NiSe2QDs的形貌为球形,尺寸小于10 nm。利用紫外可见光谱(UV-Vis)研究了BPE-NiSe2QDs的光学性质,发现其在329 nm处有一个吸收带,对应的能带值为2.99 eV。电化学实验采用差分脉冲伏安法进行。Au/BPE-NiSe2QDs/ nafion电化学传感器对0.76 V的奈韦拉平有明显的阳极响应。结果表明,在0 ~ 1.21 pM (0 ~ 0.322 ng/L)范围内,氧化峰电流随奈韦拉平浓度的增加呈线性增加,低检出限(LOD)为0.024 pM (0.0064 ng/L),灵敏度为5.52µa /pM。这些特殊的性质与已经报道的用于复杂矩阵的传感器相当,甚至更好。该电化学传感器具有较高的重复性和稳定性。该传感器成功地用于加标废水样品中奈韦拉平的检测,结果令人满意。
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引用次数: 2
Determination of o-Aminophenol by Novel Co(II) Phthalocyanine with Appliance of Composite MWCNTs 复合纳米碳纳米管应用新型Co(II)酞菁测定邻氨基酚
IF 3.1 4区 化学 Q2 Chemistry Pub Date : 2022-12-22 DOI: 10.1007/s12678-022-00804-9
T. M. Sharanakumar,  Mounesh, N Y Praveen Kumar, KR Venugopala Reddy, A. Sunilkumar

A novel peripherally tetra naphthol substituted Co(II) phthalocyanine (NCoPc) was synthesized by the reaction of naphthol linked phthalonitrile, and cobalt chloride, in the presence of catalytic amount of DMF, DBU, and K2CO3. The NCoPc and its composite with MWCNTs were characterized by FTIR, NMR, UV–Vis, XRD, TGA, and mass spectroscopic techniques. The NCoPc and NCoPc-MWCNTs-coated glassy carbon electrodes (GCEs) were used to electrochemically detect and quantify ortho amino phenol (oAP) oAP in aqueous solutions. Cyclic voltammetric data established a linear response between the oAP oxidation current (ipa) and its molar concentration (10–190 μM). The limit of detection (LoD) of the two modified electrodes was comparable (1.5 μM and 25 nM, respectively). The NCoPc and NCoPc-MWCNTs-GCEs (in the concentration range of 10–160 μM) were both low and comparable. The LoD values for oAP at the NCoPc-GCE and NCoPc-MWCNTs by DPV were 1.2 µM and 42 nM and CA were 10 nM and 6.5 nM, respectively. They are exhibited good electrocatalytic activity towards the oxidation of oAP, and this was aided by the improved conductivity of the composite modifiers.

Graphical Abstract

在DMF、DBU和K2CO3的催化作用下,以萘酚连接的邻苯二腈和氯化钴为原料,合成了一种新型的外周四萘酚取代的Co(II)酞菁(NCoPc)。采用FTIR、NMR、UV-Vis、XRD、TGA和质谱等技术对NCoPc及其与MWCNTs的复合材料进行了表征。采用NCoPc和NCoPc- mwcnts包覆的玻碳电极(GCEs)对水溶液中的邻位氨基酚(oAP)进行了电化学检测和定量。循环伏安数据表明oAP氧化电流(ipa)与其摩尔浓度(10 ~ 190 μM)呈线性关系。两种修饰电极的检出限(LoD)相当(分别为1.5 μM和25 nM)。NCoPc和NCoPc- mwcnts - gce(浓度范围在10 ~ 160 μM)均较低且具有可比性。DPV对NCoPc-GCE和NCoPc-MWCNTs的oAP LoD值分别为1.2µM和42 nM, CA为10 nM和6.5 nM。它们对oAP的氧化表现出良好的电催化活性,这得益于复合改性剂的导电性的提高。图形抽象
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引用次数: 0
Electrocatalytic Performance of Nickel Hydroxide-Decorated Microporous Nanozeolite Beta-Modified Carbon Paste Electrode for Formaldehyde Oxidation 羟基镍修饰微孔纳米沸石修饰碳糊电极对甲醛氧化的电催化性能
IF 3.1 4区 化学 Q2 Chemistry Pub Date : 2022-12-21 DOI: 10.1007/s12678-022-00799-3
Samira Eshagh-Nimvari, Seyed Karim Hassaninejad-Darzi

In this paper, aluminosilicate nanozeolite beta has been prepared and described using X-ray diffraction (XRD), nitrogen sorption isotherm, Fourier transform infrared (FT-IR), transmission electron micrograph (TEM), and field emission scanning electronic microscopy (FESEM) techniques; TEM image demonstrated semispherical particles with dimensions under 50 nm. The BET surface area, total pore volume, and pore diameter of it were attained to be 321 m2 g−1, 0.053 cm3 g−1, and 1.22 nm, respectively. The modified carbon paste electrode by aluminosilicate nanozeolite beta and nickel hydroxide (Ni(OH)2-Beta/CPE) was applied for formaldehyde (HCHO) electrocatalytic oxidation. The obtained results specify that Ni(OH)2-Beta/CPE demonstrates worthy electrocatalytic activity for oxidation of HCHO due to mesoporous construction and the great surface area of nanozeolite. The electron-transfer coefficient, catalytic rate constant, and diffusion coefficient are found to be 0.69, 2.08 × 106 cm3 mol−1 s−1, and 4.4 × 10−7 cm2 s−1, respectively. The Ni(OH)2-Beta/CPE exhibited low background current, simplicity of surface renewal, good reproducibility, and stability and also displayed high stability up to 300 cycles and 3000 s without an important loss in the current density. This modified electrode has better poisoning tolerance capability than bare CPE for HCHO electrocatalytic oxidation and is a higher device for the long term accomplishment.

本文采用x射线衍射(XRD)、氮吸附等温线、傅里叶变换红外(FT-IR)、透射电子显微镜(TEM)和场发射扫描电子显微镜(FESEM)等技术对铝硅酸盐纳米沸石β进行了制备和表征;TEM图像显示尺寸在50 nm以下的半球形颗粒。得到的BET比表面积为321 m2 g−1,总孔容为0.053 cm3 g−1,孔径为1.22 nm。采用铝硅酸盐纳米沸石和氢氧化镍(Ni(OH)2- β /CPE)改性碳糊电极对甲醛(HCHO)进行电催化氧化。结果表明,由于Ni(OH)2-Beta/CPE的介孔结构和纳米沸石的大表面积,对HCHO的氧化具有良好的电催化活性。电子转移系数、催化速率常数和扩散系数分别为0.69、2.08 × 106 cm3 mol−1 s−1和4.4 × 10−7 cm2 s−1。Ni(OH)2-Beta/CPE具有背景电流小、表面更新简单、重现性好、稳定性好等特点,在300次循环和3000 s内具有较高的稳定性,且电流密度没有明显损失。该修饰电极对HCHO电催化氧化具有比裸CPE更好的耐中毒能力,是一种长期完成的较高的装置。
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引用次数: 1
Sea Urchin–Like CoS2@WS2/NF Bifunctional Catalyst for Efficient Overall Water Splitting 类海胆CoS2@WS2/NF双功能催化剂高效整体水分解
IF 3.1 4区 化学 Q2 Chemistry Pub Date : 2022-12-19 DOI: 10.1007/s12678-022-00800-z
Chenzi Zhu, Hongbao Liu, Youchao Song, Jiajia Wang, Yuming Zhou, Yiwei Zhang

Metal sulfides have been shown to exhibit better electrical conductivity, mechanical and thermal stability, and higher electrochemical activity than their corresponding metal oxide counterparts. The one-dimensional nanoclusters and three-dimensional microspheres were assembled together by a well-designed synthetic strategy to finally form a sea urchin-like CoS2@WS2/NF composite electrode material. The stable chemical properties and firm physical structure remain stable before and after the catalytic reaction, and the unique structure, sea urchin-like morphology, is conducive to mass transfer and gas release during the reaction. In this nanocomposite, one-dimensional nanoclusters provide efficient electron transfer, while three-dimensional nanospheres provide strong and reliable mechanical support. When CoS2@WS2/NF was used as a bifunctional electrocatalyst at a current density of 10 mA cm−2 in 1.0 M KOH aqueous solution, it exhibited overpotentials as low as 127 mV and 415 mV to drive hydrogen evolution reaction (HER) and HER, respectively. Oxygen evolution reaction (OER) is responsive while having high durability. When evaluated as a two-electrode system, it delivers a small value of 1.66 V up to 10 mA cm−2, further demonstrating the superiority of the bifunctional water release function.

与金属氧化物相比,金属硫化物具有更好的导电性、机械稳定性和热稳定性以及更高的电化学活性。通过精心设计的合成策略,将一维纳米团簇和三维微球组装在一起,最终形成海胆样CoS2@WS2/NF复合电极材料。稳定的化学性质和牢固的物理结构在催化反应前后保持稳定,独特的结构,海胆样形态,有利于反应过程中的传质和气体释放。在这种纳米复合材料中,一维纳米团簇提供了高效的电子传递,而三维纳米球提供了强大可靠的机械支持。当CoS2@WS2/NF作为双功能电催化剂,在1.0 M KOH水溶液中,电流密度为10 mA cm−2时,其过电位低至127 mV和415 mV,分别驱动析氢反应(HER)和析氢反应(HER)。析氧反应(OER)反应灵敏,耐久性高。当被评估为双电极系统时,它提供了1.66 V的小值,高达10 mA cm - 2,进一步证明了双功能水释放功能的优越性。
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引用次数: 2
Crystal Size Dependence of the Photo-Electrochemical Water Oxidation on Nanoparticulate CaTiO3 电化学水氧化对纳米CaTiO3晶粒大小的影响
IF 3.1 4区 化学 Q2 Chemistry Pub Date : 2022-12-19 DOI: 10.1007/s12678-022-00801-y
Monika Klusáčková, Roman Nebel, Kateřina Minhová Macounová, Petr Krtil

Nanocrystalline CaTiO3 materials with controlled particle size were prepared using spray-freezing/freeze-drying approach utilizing gelatine as a structure-directing agent. The resulting materials show characteristic particle size between 19 and 60 nm. The shape of the nanocrystals changes from cube-like single crystal containing particles into less regular isometric particles. Prepared materials as identified by X-ray diffraction analysis are formed by orthorhombic perovskite with small admixture of cubic phase. The ratio of both perovskite phases is independent of the particle size or prevailing crystal shape. All prepared materials show n-semiconducting character with band gap of ca 3.6 eV. They also show photo-electrochemical activity in water oxidation in acid media if a bias greater than 400 mV with respect to the flat band potential is applied. The specific photo-electrochemical activity decreases with increasing specific surface area. This behavior is attributed to increased probability of the electron transfer at the illuminated CaTiO3 surface facilitated by the surface states. The CaTiO3 materials also generate significant amount of ozone upon illumination in oxygen saturated solutions. The tendency to form ozone increases with increasing particle size suggesting that the ozone formation is hindered on materials with large number of low dimensionality states (crystal edges and vertices).

Graphical Abstract

以明胶为结构导向剂,采用喷雾冷冻/冷冻干燥法制备了粒径可控的CaTiO3纳米晶材料。所得材料的特征粒径在19 ~ 60 nm之间。纳米晶体的形状从含有颗粒的立方体状单晶转变为不太规则的等距颗粒。经x射线衍射分析,所制备的材料由正交钙钛矿和少量立方相的混合物组成。两种钙钛矿相的比例与颗粒大小或晶体形状无关。所制备的材料均具有n-半导体特性,带隙约为3.6 eV。如果相对于平带电位施加大于400 mV的偏置,它们在酸性介质中的水氧化中也显示出光电化学活性。比光化学活性随比表面积的增加而降低。这种行为是由于表面状态促进了CaTiO3表面上电子转移的可能性增加。CaTiO3材料在饱和氧溶液中光照后也会产生大量的臭氧。臭氧的形成倾向随着颗粒尺寸的增加而增加,这表明臭氧的形成在具有大量低维状态(晶体边缘和顶点)的材料上受到阻碍。图形抽象
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引用次数: 0
期刊
Electrocatalysis
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