Abstract
Non-precious electro catalysts with high-efficiency, cheapness and stablility are of great significance to replace noble metal electro catalysts in the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). In this work, triangular Cu@CuO nanorods on Cu nanosheets were fabricated by a novel in-situ oxidation approach using Cu nanosheets as self-template and conductive nano-substrate in an aqueous solution of NaOH/H2O2, and then by low-temperature phosphorization treatments. The experimental results show that the phosphating temperature has a significant effect on the morphology, composition and number of active sites of Cu@Cu3P nanorods. The Cu@Cu3P-280 electrode exhibits a good HER catalytic activity of achieving a current density of 10 mA/cm2 at 252 mV in acid electrolyte. After catalysis for 14 h, the current density can still reach 72% of the initial value. Moreover, the Cu@Cu3P-280 electrode also shows an excellent OER catalytic activity in basic electrolyte, reaching a current density of 10 mA/cm2 at the overpotential value of 200 mV. After catalysis for 12 h, the current density remained more than 93% of the initial value. This work provides a theoretical basis for the directional design and preparation of sustainable, low-cost, bifunctional electrocatalytic materials.
摘要
开发能够取代贵金属的高效、廉价、稳定的非贵金属催化剂,对于推动电催化水裂解析氢、析氧技术的发展具有重要意义。本文以铜纳米片为模板和导电基底,H2O2为氧源,NaOH 为pH 调节剂,通过原位氧化的方法在Cu 纳米片表面构筑三角柱状结构的Cu@CuO, 再对Cu@CuO 进行低温磷化,获得三角纳米柱状Cu@Cu3P。实验结果表明,磷化温度在调节Cu@Cu3P 纳米柱阵列的形貌、组成及活性位点数量方面具有显著效果。当磷化温度为280 ℃时,可获得形貌均一、活性高的纳米三角柱状阵列结构材料(Cu@Cu3P-280)。Cu@Cu3P-280 电极在0.5 mol/L H2SO4 电解质中表现出良好的析氢催化活性,在电流密度为10 mA/cm2时,其过电位为252 mV,催化14 h 后,电流密度仍可达初始值的72%。Cu@Cu3P-280 电极在1 mol/L KOH 电解质中也展现出优异的催化析氧活性,当电流密度为10 mA/cm2时,其过电位仅为200 mV,催化12 h 后,电流密度保持初始值的93%。此研究为可持续、低价、双功能电催化材料的定向设计与制备提供理论基础。
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WANG Mao-sen, FU Wen-ying, DU Lei, et al. Surface engineering by doping manganese into cobalt phosphide towards highly efficient bifunctional HER and OER electrocatalysis [J]. Applied Surface Science, 2020, 515: 146059. DOI: https://doi.org/10.1016/j.apsusc.2020.146059.
YAN Hai-jing, XIE Ying, WU Ai-ping, et al. Anionmodulated HER and OER activities of 3D Ni-V-based interstitial compound heterojunctions for high-efficiency and stable overall water splitting [J]. Advanced Materials (Deerfield Beach, Fla), 2019, 31(23): e1901174. DOI: https://doi.org/10.1002/adma.201901174.
ALOBAID A, WANG Chun-sheng, ADOMAITIS R A. Mechanism and kinetics of HER and OER on NiFe LDH films in an alkaline electrolyte [J]. Journal of the Electrochemical Society, 2018, 165(15): J3395–J3404. DOI: https://doi.org/10.1149/2.0481815jes.
ENSAFI A A, JAFARI-ASL M, NABIYAN A, et al. Ni3S2/ball-milled silicon flour as a bi-functional electrocatalyst for hydrogen and oxygen evolution reactions [J]. Energy, 2016, 116: 392–401. DOI: https://doi.org/10.1016/j.energy.2016.09.128.
JIANG Hao, GU Jin-xing, ZHENG Xu-sheng, et al. Defect-rich and ultrathin N doped carbon nanosheets as advanced trifunctional metal-free electrocatalysts for the ORR, OER and HER [J]. Energy & Environmental Science, 2019, 12(1): 322–333. DOI: https://doi.org/10.1039/C8EE03276A.
SILVA V D, DA SILVA F E F, DE MEDEIROS E S, et al. Catalysts for hydrogen and oxygen evolution reactions (HER/OER) in cells [M]//Heterogeneous Catalysis. Amsterdam: Elsevier, 2022: 457 - 470. DOI: https://doi.org/10.1016/b978-0-323-85612-6.00016-4.
CHENG Jin-bin, ZHANG Hua-min, MA Hai-peng, et al. Study of carbon-supported IrO2 and RuO2 for use in the hydrogen evolution reaction in a solid polymer electrolyte electrolyzer [J]. Electrochimica Acta, 2010, 55(5): 1855–1861. DOI: https://doi.org/10.1016/j.electacta.2009.10.081.
CHEREVKO S, GEIGER S, KASIAN O, et al. Oxygen and hydrogen evolution reactions on Ru, RuO2, Ir, and IrO2 thin film electrodes in acidic and alkaline electrolytes: A comparative study on activity and stability [J]. Catalysis Today, 2016, 262: 170–180. DOI: https://doi.org/10.1016/j.cattod.2015.08.014.
WANG Ya-rong, WANG Zhang-jun, JIN Chao, et al. Enhanced overall water electrolysis on a bifunctional perovskite oxide through interfacial engineering [J]. Electrochimica Acta, 2019, 318: 120–129. DOI: https://doi.org/10.1016/j.electacta.2019.06.073.
HAO Shao-yun, WANG Ya-hui, ZHENG Guo-kui, et al. Tuning electronic correlations of ultra-small IrO2 nanoparticles with La and Pt for enhanced oxygen evolution performance and long-durable stability in acidic media [J]. Applied Catalysis B: Environmental, 2020, 266: 118643. DOI: https://doi.org/10.1016/j.apcatb.2020.118643.
SUNG M, KIM J. Oxygen evolution reaction on Pt sphere and Ir-modified Pt sphere electrodes with porous structures [J]. International Journal of Hydrogen Energy, 2018, 43(4): 2130–2138. DOI: https://doi.org/10.1016/j.ijhydene.2017.11.167.
DIAO Fang-yuan, HUANG Wei, CTISTIS G, et al. Bifunctional and self-supported NiFeP-layer-coated NiP rods for electrochemical water splitting in alkaline solution [J]. ACS Applied Materials & Interfaces, 2021, 13(20): 23702–23713. DOI: https://doi.org/10.1021/acsami.1c03089.
LUO Shan-shan, WANG Ran, HEI Peng, et al. Self-assembled Ni2P nanosheet-implanted reduced graphene oxide composite as highly efficient electrocatalyst for oxygen evolution reaction [J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 612: 125992. DOI: https://doi.org/10.1016/j.colsurfa.2020.125992.
SU Zhe, LU Ying-jiong, SRINIVAS K, et al. Carbon nanotubes-interconnected heterostructural FeP/Ni2P nanospindles as efficient and stable electrocatalysts for oxygen evolution reaction [J]. Journal of Alloys and Compounds, 2021, 883: 160926. DOI: https://doi.org/10.1016/j.jallcom.2021.160926.
YANG Fang, CHEN Xin, LI Zhe, et al. Ultrathin FeP nanosheets as an efficient catalyst for electrocatalytic water oxidation: Promoted intermediates adsorption by surface defects [J]. ACS Applied Energy Materials, 2020, 3(4): 3577–3585. DOI: https://doi.org/10.1021/acsaem.0c00080.
XIONG De-hua, WANG Xiao-guang, LI Wei, et al. Facile synthesis of iron phosphide nanorods for efficient and durable electrochemical oxygen evolution [J]. Chemical Communications, 2016, 52(56): 8711–8714. DOI: https://doi.org/10.1039/C6CC04151E.
WANG Ke-wei, TAN Jin-shan, LU Ze-jia, et al. Nanoscale engineering MoP/Fe2P/RGO toward efficient electrocatalyst for hydrogen evolution reaction [J]. International Journal of Hydrogen Energy, 2018, 43(30): 13939–13945. DOI: https://doi.org/10.1016/j.ijhydene.2018.02.012.
JIAO Yan-qing, YAN Hai-jing, WANG Rui-hong, et al. Porous plate-like MoP assembly as an efficient pH-universal hydrogen evolution electrocatalyst [J]. ACS Applied Materials & Interfaces, 2020, 12(44): 49596–49606. DOI: https://doi.org/10.1021/acsami.0c13533.
ZHOU Ze-qi, MAHMOOD N, ZHANG Yong-chao, et al. CoP nanoparticles embedded in P and N co-doped carbon as efficient bifunctional electrocatalyst for water splitting [J]. Journal of Energy Chemistry, 2017, 26(6): 1223–1230. DOI: https://doi.org/10.1016/j.jechem.2017.07.021.
ZHUANG Ming-hao, OU Xue-wu, DOU Yu-bing, et al. Polymer-embedded fabrication of Co2P nanoparticles encapsulated in N, P-doped graphene for hydrogen generation [J]. Nano Letters, 2016, 16(7): 4691–4698. DOI: https://doi.org/10.1021/acs.nanolett.6b02203.
JIN Zhao-yu, LI Pan-pan, XIAO Dan. Metallic Co2P ultrathin nanowires distinguished from CoP as robust electrocatalysts for overall water-splitting [J]. Green Chemistry, 2016, 18(6): 1459–1464. DOI: https://doi.org/10.1039/C5GC02462E.
KIM B K, KIM S K, CHO S K, et al. Enhanced catalytic activity of electrodeposited Ni-Cu-P toward oxygen evolution reaction [J]. Applied Catalysis B: Environmental, 2018, 237: 409–415. DOI: https://doi.org/10.1016/j.apcatb.2018.05.082.
LIU Zi-xuan, WANG Xiao-long, HU Ai-ping, et al. 3D Sedoped NiCoP nanoarrays on carbon cloth for efficient alkaline hydrogen evolution [J]. Journal of Central South University, 2021, 28(8): 2345–2359. DOI: https://doi.org/10.1007/s11771-021-4774-y.
MONDAL I, MAHATA A, KIM H, et al. A combined experimental and theoretical approach revealing a direct mechanism for bifunctional water splitting on doped copper phosphide [J]. Nanoscale, 2020, 12(34): 17769–17779. DOI: https://doi.org/10.1039/d0nr03414b.
PI Ming-yu, ZHANG Ding-ke, WANG Shu-xia, et al. Enhancing electrocatalytic hydrogen evolution of WP2 three-dimensional nanowire arrays via Mo doping [J]. Materials Letters, 2018, 213: 315–318. DOI: https://doi.org/10.1016/j.matlet.2017.11.058.
NKABINDE S S, MWONGA P V, MPELANE S, et al. Phase-dependent electrocatalytic activity of colloidally synthesized WP and α-WP2 electrocatalysts for hydrogen evolution reaction [J]. New Journal of Chemistry, 2021, 45(34): 15594–15606. DOI: https://doi.org/10.1039/D1NJ00927C.
LIU Wei, GENG Peng, LI Shi-qing, et al. Tuning electronic configuration of WP2 nanosheet arrays via nickel doping for high-efficiency hydrogen evolution reaction [J]. Journal of Energy Chemistry, 2021, 55: 17–24. DOI: https://doi.org/10.1016/j.jechem.2020.06.068.
LIU Wei, GENG Peng, LI Shi-qing, et al. Self-supported three-dimensional WP2 (WP) nanosheet arrays for efficient electrocatalytic hydrogen evolution [J]. International Journal of Hydrogen Energy, 2020, 45(53): 28576–28585. DOI: https://doi.org/10.1016/j.ijhydene.2020.07.144.
PFEIFFER H, TANCRET F, BICHAT M P, et al. Air stable copper phosphide (Cu3P): A possible negative electrode material for lithium batteries [J]. Electrochemistry Communications, 2004, 6(3): 263–267. DOI: https://doi.org/10.1016/j.elecom.2003.12.012.
WANG Rui, DONG Xi-yan, DU Jiao, et al. MOF-derived bifunctional Cu3 P nanoparticles coated by a N, P-codoped carbon shell for hydrogen evolution and oxygen reduction [J]. Advanced Materials, 2018, 30(6): 1703711. DOI: https://doi.org/10.1002/adma.201703711.
ZHOU Xin, ZHOU Xiao-liang, LIU Li-min, et al. Self-supported Cu3P nanowire electrode as an efficient electrocatalyst for the oxygen evolution reaction [J]. RSC Advances, 2021, 11(54): 34137–34143. DOI: https://doi.org/10.1039/D1RA05526G.
TIAN Jing-qi, LIU Qian, CHENG Ning-yan, et al. Self-supported Cu3P nanowire arrays as an integrated high-performance three-dimensional cathode for generating hydrogen from water [J]. Angewandte Chemie, 2014, 53(36): 9577–9581. DOI: https://doi.org/10.1002/anie.201403842.
WEI Shu-ting, QI Kun, JIN Zhao, et al. One-step synthesis of a self-supported copper phosphide nanobush for overall water splitting [J]. ACS Omega, 2016, 1(6): 1367–1373. DOI: https://doi.org/10.1021/acsomega.6b00366.
DANG Rui, SONG Ling-ling, DONG Wen-jun, et al. Synthesis and self-assembly of large-area Cu nanosheets and their application as an aqueous conductive ink on flexible electronics [J]. ACS Applied Materials & Interfaces, 2014, 6(1): 622–629. DOI: https://doi.org/10.1021/am404708z.
ZHANG Ke, XIONG Zhi-ping, LI Shu-min, et al. Cu3P/RGO promoted Pd catalysts for alcohol electro-oxidation [J]. Journal of Alloys and Compounds, 2017, 706: 89–96. DOI: https://doi.org/10.1016/j.jallcom.2017.02.179.
HOU Chun-chao, CHEN Qian-qian, WANG Chuan-jun, et al. Self-supported cedarlike semimetallic Cu3P nanoarrays as a 3D high-performance Janus electrode for both oxygen and hydrogen evolution under basic conditions [J]. ACS Applied Materials & Interfaces, 2016, 8(35): 23037–23048. DOI: https://doi.org/10.1021/acsami.6b06251.
ZHEN Wen-long, JIAO Wen-jun, WU Yu-qi, et al. The role of a metallic copper interlayer during visible photocatalytic hydrogen generation over a Cu/Cu2O/Cu/TiO2 catalyst [J]. Catalysis Science & Technology, 2017, 7(21): 5028–5037. DOI: https://doi.org/10.1039/C7CY01432E.
FU Zhong-yuan, MA Xin-yi, XIA Bing, et al. Efficient photocatalytic H2 evolution over Cu and Cu3P co-modified TiO2 nanosheet [J]. International Journal of Hydrogen Energy, 2021, 46(37): 19373–19384. DOI: https://doi.org/10.1016/j.ijhydene.2021.03.089.
ZHANG Hong-wei, TAN Hui-ru, JAENICKE S, et al. Highly efficient and robust Cu catalyst for non-oxidative dehydrogenation of ethanol to acetaldehyde and hydrogen [J]. Journal of Catalysis, 2020, 389: 19–28. DOI: https://doi.org/10.1016/j.jcat.2020.05.018.
LIN Jia, ZENG Cheng-hui, LIN Xiao-ming, et al. CNT-assembled octahedron carbon-encapsulated Cu3P/Cu heterostructure by in situ MOF-derived engineering for superior lithium storage: Investigations by experimental implementation and first-principles calculation [J]. Advanced Science (Weinheim, Baden-Wurttemberg, Germany), 2020, 7(14): 2000736. DOI: https://doi.org/10.1002/advs.202000736.
KOU Yu-li, WANG Kang-kang, WUMAER M, et al. Synthesis of hollow Cu@Cu3 P core-shell nanostructure as dual-functional catalyst with copper vacancy for enhancing chemical reduction and photocatalytic performance [J]. Applied Surface Science, 2022, 589: 153031. DOI: https://doi.org/10.1016/j.apsusc.2022.153031.
LI Xiao-lin, ZHANG Jia-ling, ZHANG Yu, et al. Copper induced phosphide for enhanced electrochemical hydrogen evolution reaction [J]. International Journal of Hydrogen Energy, 2020, 45(41): 21422–21430. DOI: https://doi.org/10.1016/j.ijhydene.2020.05.213.
MA Lian-bo, SHEN Xiao-ping, ZHOU Hu, et al. Synthesis of Cu3P nanocubes and their excellent electrocatalytic efficiency for the hydrogen evolution reaction in acidic solution [J]. RSC Advances, 2016, 6(12): 9672–9677. DOI: https://doi.org/10.1039/C5RA24427G.
HAO Jin-hui, YANG Wen-shu, HUANG Zhi-peng, et al. Superhydrophilic and superaerophobic copper phosphide microsheets for efficient electrocatalytic hydrogen and oxygen evolution [J]. Advanced Materials Interfaces, 2016, 3(16): 1600236. DOI: https://doi.org/10.1002/admi.201600236.
RONG Jian, XU Jin-chao, QIU Feng-xian, et al. Sea urchinlike MOF-derived formation of porous Cu3P@C as an efficient and stable electrocatalyst for oxygen evolution and hydrogen evolution reactions [J]. Advanced Materials Interfaces, 2019, 6(14): 1900502. DOI: https://doi.org/10.1002/admi.201900502.
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DANG Rui provided the concept and edited the draft of manuscript. DANG Rui and XU Xiufeng validated the proposed method with practical experiments. XIE Meng-meng accomplished writing-review and editing. All authors have read and agreed to the published version of the manuscript.
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DANG Rui, XU Xiu-feng and XIE Mengmeng declare that they have no conflict of interest.
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Dang, R., Xu, Xf. & Xie, Mm. Fabrication of triangular Cu3P nanorods on Cu nanosheets as electrocatalyst for boosted electrocatalytic water splitting. J. Cent. South Univ. 29, 3870–3883 (2022). https://doi.org/10.1007/s11771-023-5243-6
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DOI: https://doi.org/10.1007/s11771-023-5243-6