微波诱导高分散Pd/FeP催化剂构筑及其电催化性能研究

doi:10.11949/0438-1157.20231388

摘要/Abstract

摘要：

微波技术作为一种新型过程强化手段，已被广泛应用于材料制备过程。利用微波对吸波型载体的选择性加热，使其产生局部高温诱导催化剂颗粒的沉积，有望构筑高分散钯（Pd）催化剂结构，而这一特殊结构对提高催化剂电催化氧化甲酸活性、提升甲酸燃料电池的性能至关重要。为探究微波诱导高分散钯催化剂便捷制备的可行性，本文首先通过水热法制备了强吸波的空心海胆状磷化铁（FeP）作为催化剂载体，而后分别在常规加热与微波加热条件下通过乙二醇还原法在FeP表面沉积Pd。使用XRD、TEM、SEM技术表征Pd/FeP产品的形貌和微观结构，探究微波加热对催化剂表面金属钯颗粒分散的影响作用。使用循环伏安法和线性伏安法评价所制备催化剂的催化活性，通过探讨催化剂结构与其电催化活性的构效关系，揭示微波合成对Pd/FeP催化剂性能的强化作用机制。研究结果表明，空心海胆状的FeP颗粒具有较强的微波吸收能力，因而在受到微波辐射时，其表面形成的局部过热诱导Pd的原位沉积，使得微波水热法制备的Pd催化剂具有良好的分散特性，然而溶剂主体温度的过高会增加Pd之间的团聚。相对于常规手段合成的催化剂，利用微波水热法在120°C下制备的催化剂电化学活性面积提升了约3.5倍，对甲酸电催化氧化活性提升了约54倍。

关键词: 微波合成, 纳米结构, 电化学, 催化剂, 粒度分布

Abstract:

As a novel method of process intensification, microwave technology has been widely used in material preparation. The selective heating characteristic of microwave-absorbing support can lead to the formation of local overheating domains, inducing the deposition of catalyst over the support surface, which is promising to construct highly dispersed Pd-based catalysts that are crucial to improve their electrocatalytic activity and therefore promote the performance of formic acid fuel cells. With the aim to explore the feasibility of facile fabrication of highly dispersed Pd-based catalysts induced by microwave, this study first prepared microwave-absorbing ferrous phosphide (FeP) particles in the shape of hollow sea urchin using a hydrothermal method to serve as catalyst support, where Pd was deposited through ethylene glycol reduction under conventional heating and microwave heating methods, respectively. XRD, TEM, and SEM technologies were used to characterize the morphology and microstructure of Pd/FeP products, and to explore the effect of microwave heating on the dispersion of metal palladium particles on the catalyst surface. The catalytic activity of the prepared catalyst was evaluated using cyclic voltammetry and linear voltammetry. By exploring the structure-activity relationship between the structure of catalysts and their electrocatalytic activity, the strengthening mechanism of microwave synthesis on the performance of Pd/FeP catalyst was revealed. The experimental results indicate that the microwave-absorbing hollow sea urchin shaped FeP can induce the in situ deposition of Pd due to the formation of local “hot spots”, inducing the generation of highly dispersed Pd-based catalysts. Compared to traditionally prepared catalysts, the electrochemical active area of these catalysts obtained from microwave synthesis has a 3.5-fold increase, while the electrocatalytic oxidation performance of formic acid increases by about 54 times.

Key words: microwave synthesis, nanostructure, electrochemistry, catalyst, size distribution

中图分类号:

TQ 032.4

李昂, 赵振宇, 李洪, 高鑫. 微波诱导高分散Pd/FeP催化剂构筑及其电催化性能研究[J]. 化工学报, 2024, 75(4): 1594-1606.

Ang LI, Zhenyu ZHAO, Hong LI, Xin GAO. Microwave induced construction of highly dispersed Pd/FeP catalysts and their electrocatalytic performance[J]. CIESC Journal, 2024, 75(4): 1594-1606.

图/表 12

图1 微波和常规加热合成Pd/FeP催化剂装置示意图1—蛇形冷凝管;2—磁子;3—带夹套的微波反应器;4—光纤温度计;5—微波炉;6—硅油入口;7—硅油出口;8—煤油温度计;9—磁力搅拌油浴锅

Fig.1 Schematic diagram of experimental apparatuses for the synthesis of Pd/FeP catalyst under microwave irradiation and conventional heating, respectively

图2 Pd/FeP催化剂的合成过程

Fig.2 The synthesis procedure of Pd/FeP catalyst

图3 α-FeOOH样品的XRD谱图

Fig.3 XRD patterns of α-FeOOH sample

图4 空心海胆状α-FeOOH的SEM图、TEM图和EDS图

Fig.4 SEM, TEM, and EDS images of hollow sea urchin shaped α-FeOOH sample

图5 FeP的介电性能

Fig.5 Dielectric performance of FeP

图6 空心海胆状FeP的SEM图、TEM图和EDS图

Fig.6 SEM, TEM, and EDS images of hollow sea urchin shaped FeP

图7 Pd/FeP的XRD谱图

Fig.7 XRD patterns of Pd/FeP

图8 常规加热制备的Pd/FeP-CH-90催化剂的SEM图和EDS图

Fig.8 SEM and EDS images of Pd/FeP-CH-90 catalyst prepared by conventional heating

图9 微波制备的Pd/FeP-MW-90催化剂的SEM图和EDS图

Fig.9 SEM and EDS images of Pd/FeP-MW-90 catalyst prepared by microwave

图10 Pd/FeP催化剂在0.5 mol/L的H2SO4 溶液中的循环伏安图

Fig.10 Cyclic voltammetry of Pd/FeP catalyst in 0.5 mol/L H2SO4 solution

图11 Pd/FeP催化剂在0.5 mol/L H2SO4+0.5 mol/L HCOOH溶液中的线性扫描伏安图

Fig.11 Linear sweep voltammetry of Pd/FeP catalyst in 0.5 mol/L H2SO4+0.5 mol/L HCOOH solution

图12 不同加热条件下制备Pd/FeP催化剂的机理和SEM图

Fig.12 Preparation of Pd/FeP catalyst under various heating conditions—mechanisms and SEM images of products

参考文献 47

1	Yang C Z, Wang T Y, Li C C, et al. PdMo bimetallene coupled with MXene nanosheets as efficient bifunctional electrocatalysts for formic acid and methanol oxidation reactions[J]. ACS Applied Materials & Interfaces, 2023, 15(42): 49195-49203.
2	Hu S Z, Gao Z Q, Gao S J, et al. Atomic ordering effect of intermetallic PdCoNi/rGO catalysts on formic acid electro-oxidation[J]. ACS Applied Energy Materials, 2023, 6(21): 11051-11060.
3	Shatla A S, Hassan K M, Abd-El-Latif A A, et al. Poly 1,5-diaminonaphthalene supported Pt, Pd, Pt/Pd and Pd/Pt nanoparticles for direct formic acid oxidation[J]. Journal of Electroanalytical Chemistry, 2019, 833: 231-241.
4	Zhang L, Wan L, Ma Y R, et al. Crystalline palladium-cobalt alloy nanoassemblies with enhanced activity and stability for the formic acid oxidation reaction[J]. Applied Catalysis B: Environmental, 2013, 138/139: 229-235.
5	Zhao L, Sui X L, Li J Z, et al. Supramolecular assembly promoted synthesis of three-dimensional nitrogen doped graphene frameworks as efficient electrocatalyst for oxygen reduction reaction and methanol electrooxidation[J]. Applied Catalysis B: Environmental, 2018, 231: 224-233.
6	Qiu B C, Cai L J, Wang Y, et al. Fabrication of nickel-cobalt bimetal phosphide nanocages for enhanced oxygen evolution catalysis[J]. Advanced Functional Materials, 2018, 28(17): 1706008.
7	Yang J, Zhang Y, Sun C C, et al. Graphene and cobalt phosphide nanowire composite as an anode material for high performance lithium-ion batteries[J]. Nano Research, 2016, 9(3): 612-621.
8	Hong W T, Jian C Y, Wang G X, et al. Self-supported nanoporous cobalt phosphosulfate electrodes for efficient hydrogen evolution reaction[J]. Applied Catalysis B: Environmental, 2019, 251: 213-219.
9	Chang J F, Feng L G, Liu C P, et al. An effective Pd-Ni₂P/C anode catalyst for direct formic acid fuel cells[J]. Angewandte Chemie (International Ed. in English), 2014, 53(1): 122-126.
10	Chang J F, Feng L G, Liu C P, et al. Ni₂P enhances the activity and durability of the Pt anode catalyst in direct methanol fuel cells[J]. Energy & Environmental Science, 2014, 7(5): 1628-1632.
11	Wang F L, Xue H G, Tian Z Q, et al. Fe₂P as a novel efficient catalyst promoter in Pd/C system for formic acid electro-oxidation in fuel cells reaction[J]. Journal of Power Sources, 2018, 375: 37-42.
12	Leng Y, Zhang C J, Liu B, et al. Synergistic activation of palladium nanoparticles by polyoxometalate-attached melem for boosting formic acid dehydrogenation efficiency[J]. ChemSusChem, 2018, 11(19): 3396-3401.
13	Bao Y F, Wang F L, Gu X C, et al. Core-shell structured PtRu nanoparticles@FeP promoter with an efficient nanointerface for alcohol fuel electrooxidation[J]. Nanoscale, 2019, 11(40): 18866-18873.
14	Zhang L L, Ding L X, Luo Y R, et al. PdO/Pd-CeO₂ hollow spheres with fresh Pd surface for enhancing formic acid oxidation[J]. Chemical Engineering Journal, 2018, 347: 193-201.
15	Wang H W, Gu X K, Zheng X S, et al. Disentangling the size-dependent geometric and electronic effects of palladium nanocatalysts beyond selectivity[J]. Science Advances, 2019, 5(1): eaat6413.
16	Zhou W J, Li M, Ding O L, et al. Pd particle size effects on oxygen electrochemical reduction[J]. International Journal of Hydrogen Energy, 2014, 39(12): 6433-6442.
17	Wei M, Zhao L, Jiang L W, et al. Development of high-throughput rapid heat-treatment and characterization process[J]. Acta Materialia, 2023, 261: 119365.
18	Kappe C O. Controlled microwave heating in modern organic synthesis[J]. Angewandte Chemie (International Ed. in English), 2004, 43(46): 6250-6284.
19	Varma R S. Journey on greener pathways: from the use of alternate energy inputs and benign reaction media to sustainable applications of nano-catalysts in synthesis and environmental remediation[J]. Green Chemistry, 2014, 16(4): 2027-2041.
20	Breeden S W, Clark J H, Farmer T J, et al. Microwave heating for rapid conversion of sugars and polysaccharides to 5-chloromethyl furfural[J]. Green Chemistry, 2013, 15(1): 72-75.
21	Demirskyi D, Agrawal D, Ragulya A. Neck growth kinetics during microwave sintering of copper[J]. Scripta Materialia, 2010, 62(8): 552-555.
22	Upadhyaya A, Tiwari S K, Mishra P. Microwave sintering of W-Ni-Fe alloy[J]. Scripta Materialia, 2007, 56(1): 5-8.
23	Ebadzadeh T, Sarrafi M H, Salahi E. Microwave-assisted synthesis and sintering of mullite[J]. Ceramics International, 2009, 35(8): 3175-3179.
24	Fidalgo B, Fernández Y, Zubizarreta L, et al. Growth of nanofilaments on carbon-based materials from microwave-assisted decomposition of CH₄ [J]. Applied Surface Science, 2008, 254(11): 3553-3557.
25	Schwenke A M, Hoeppener S, Schubert U S. Synthesis and modification of carbon nanomaterials utilizing microwave heating[J]. Advanced Materials, 2015, 27(28): 4113-4141.
26	陈婷, 胡泽浩, 秦喆, 等. 有机相微波合成AgInS₂量子点及其白光发光二极管应用研究[J]. 化工学报, 2022,73(11): 5167-5176.
	Chen T, Hu Z H, QIN Z, et al. Microwave synthesis of AgInS₂ quantum dots in organic solvent and application for white light-emitting diodes[J]. CIESC Journal, 2022, 73(11): 5167-5176.
27	Xu W T, Zhou J C, Su Z M, et al. Microwave catalytic effect: a new exact reason for microwave-driven heterogeneous gas-phase catalytic reactions[J]. Catalysis Science & Technology, 2016, 6(3): 698-702.
28	Luo M D, Zhou J C, Xu W T, et al. Development of composite microwave catalysts (ABS _x /CNTs, A = Co, B = Ni, Mo) for the highly effective direct decomposition of H₂S into H₂ and S[J]. Fuel, 2020, 281: 118729.
29	Rodríguez A M, Prieto P, de la Hoz A, et al. Influence of polarity and activation energy in microwave-assisted organic synthesis (MAOS)[J]. ChemistryOpen, 2015, 4(3): 308-317.
30	Dudley G B, Richert R, Stiegman A E. On the existence of and mechanism for microwave-specific reaction rate enhancement[J]. Chemical Science, 2015, 6(4): 2144-2152.
31	Horikoshi S, Serpone N. Role of microwaves in heterogeneous catalytic systems[J]. Catalysis Science & Technology, 2014, 4(5): 1197-1210.
32	Horikoshi S, Osawa A, Abe M, et al. On the generation of hot-spots by microwave electric and magnetic fields and their impact on a microwave-assisted heterogeneous reaction in the presence of metallic Pd nanoparticles on an activated carbon support[J]. The Journal of Physical Chemistry C, 2011, 115(46): 23030-23035.
33	Zhao Z Y, Shen X, Li H, et al. Watching microwave-induced microscopic hot spots via the thermosensitive fluorescence of europium/terbium mixed-metal organic complexes[J]. Angewandte Chemie (International Ed. in English), 2022, 61(6): e202114340.
34	Mu S Y, Liu K, Li H, et al. Microwave-assisted synthesis of highly dispersed ZrO₂ on CNTs as an efficient catalyst for producing 5-hydroxymethylfurfural (5-HMF)[J]. Fuel Processing Technology, 2022, 233: 107292.
35	Buinachev S, Mashkovtsev M A, Zhirenkina N, et al. A new approach for the synthesis of monodisperse zirconia powders with controlled particle size[J]. International Journal of Hydrogen Energy, 2021, 46(32): 16878-16887.
36	Xiao S N, Zhou C, Ye X Y, et al. Solid-phase microwave reduction of WO₃ by GO for enhanced synergistic photo-Fenton catalytic degradation of bisphenol A[J]. ACS Applied Materials & Interfaces, 2020, 12(29): 32604-32614.
37	Huang H W, Zhou S, Yu C, et al. Rapid and energy-efficient microwave pyrolysis for high-yield production of highly-active bifunctional electrocatalysts for water splitting[J]. Energy & Environmental Science, 2020, 13(2): 545-553.
38	Zhao B, Shao G, Fan B B, et al. Synthesis of flower-like CuS hollow microspheres based on nanoflakes self-assembly and their microwave absorption properties[J]. Journal of Materials Chemistry A, 2015, 3(19): 10345-10352.
39	Wen C Y, Li X, Zhang R X, et al. High-density anisotropy magnetism enhanced microwave absorption performance in Ti₃C₂T _x MXene@Ni microspheres[J]. ACS Nano, 2022, 16(1): 1150-1159.
40	Li B D, Zeng Z H, Qiao J, et al. Hollow ZnO/Fe₃O₄@C nanofibers for efficient electromagnetic wave absorption[J]. ACS Applied Nano Materials, 2022, 5(8): 11617-11626.
41	Elhassan A, Abdalla I, Yu J Y, et al. Microwave-assisted fabrication of sea cucumber-like hollow structured composite for high-performance electromagnetic wave absorption[J]. Chemical Engineering Journal, 2020, 392: 123646.
42	Zheng Q, Cao W Q, Zhai H Z, et al. Tailoring carbon-based nanofiber microstructures for electromagnetic absorption, shielding, and devices[J]. Materials Chemistry Frontiers, 2023, 7(9): 1737-1759.
43	Ji T, Tu R, Mu L W, et al. Structurally tuning microwave absorption of core/shell structured CNT/polyaniline catalysts for energy efficient saccharide-HMF conversion[J]. Applied Catalysis B: Environmental, 2018, 220: 581-588.
44	Wang F L, Yang X D, Dong B X, et al. A FeP powder electrocatalyst for the hydrogen evolution reaction[J]. Electrochemistry Communications, 2018, 92: 33-38
45	Tian L H, Yan X D, Chen X B. Electrochemical activity of iron phosphide nanoparticles in hydrogen evolution reaction[J]. ACS Catalysis, 2016, 6(8): 5441-5448.
46	Wang B, Wu H B, Yu L, et al. Template-free formation of uniform urchin-like α-FeOOH hollow spheres with superior capability for water treatment[J]. Advanced Materials, 2012, 24(8): 1111-1116.
47	王亭杰, 金涌, 汪展文, 等. 针状羟基氧化铁的成核与生长过程[J]. 化工学报, 1998, 49(2): 201-207.
	Wang T J, Jin Y, Wang Z W, et al. Nucleation and growth process of the needle-like goethite crystals[J]. Journal of Chemical Industry and Engineering (China), 1998, 49(2): 201-207.

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