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Research Article

High-entropy selenides: A new platform for highly selective oxidation of glycerol to formate and energy-saving hydrogen evolution in alkali-acid hybrid electrolytic cell

Hu Yao1, Yibo Wang2, Yinan Zheng1, Xin Yu1, Junjie Ge2, Yonghong Zhu3( ), Xiaohui Guo1( )
Key Lab of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, The College of Chemistry and Materials Science, Northwest University, Xi’an 710069, China
Changchun Institute of Applied Chemistry, Changchun 130022, China
School of Chemical Engineering, Northwest University, Xi’an 710069, China
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Graphical Abstract

A kind of advanced high-entropy selenide (HESe) electrocatalysts were prepared by in-situ growth on copper foam (CF) for the first time. High-entropy selenide catalyst exhibits high selectivity for formate in glycerol oxidation reaction (GOR) and very low potential ~ 0.5 V in electrolysis hydrogen generation and robust operation stability.

Abstract

Glycerol oxidation reaction (GOR) coupled with hydrogen generation simultaneously is a promising strategy for developing sustainable energy conversion technologies, but the complexity of glycerol oxidation products and the high coupling hydrogen evolution potential limit its wide application. In this paper, a self-supported high-entropy selenide electrode can be fabricated via a simple hydrothermal process. Then, the prepared electrode as an advanced catalyst displays optimal catalytic activity (1.20 V at 10 mA·cm−2) and high selectivity for the formation of formate in GOR. The results show that the lattice distortion effect of high entropy materials composed of multiple elements is mainly responsible for the greatly improved catalytic activity and selectivity for GOR. Moreover, an advanced alkali-acid hybrid electrolytic cell was assembled that enables efficient energy-saving hydrogen generation and GOR simultaneously. Herein, the electrolyzer requires only 0.5 V applied voltage to reach 10 mA·cm−2 for hydrogen generation and maintains long-term operation stability.

Keywords

high-entropy selenideslattice distortionglycerol oxidation reaction (GOR)formateactivity

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References

[1]

Li, X. J.; Zhang, H. K.; Li, X.; Hu, Q.; Deng, C.; Jiang, X. X.; Yang, H. P.; He, C. X. Janus heterostructure of cobalt and iron oxide as dual-functional electrocatalysts for overall water splitting. Nano Res. 2023, 16, 2245–2251.
Crossref Google Scholar
[2]

Fan, L. F.; Ji, Y. X.; Wang, G. X.; Chen, J. X.; Chen, K.; Liu, X.; Wen, Z. H. High entropy alloy electrocatalytic electrode toward alkaline glycerol valorization coupling with acidic hydrogen production. J. Am. Chem. Soc. 2022, 144, 7224–7235.
Crossref Google Scholar
[3]

Geng, S.; Tian, F. Y.; Li, M. G.; Liu, Y. Q.; Sheng, J.; Yang, W. W.; Yu, Y. S.; Hou, Y. L. Activating interfacial S sites of MoS2 boosts hydrogen evolution electrocatalysis. Nano Res. 2022, 15, 1809–1816.
Crossref Google Scholar
[4]

Han, J. Y.; Guan, J. Q. Multicomponent transition metal oxides and (oxy)hydroxides for oxygen evolution. Nano Res. 2023, 16, 1913–1966.
Crossref Google Scholar
[5]

Shang, H. S.; Liu, D. Atomic design of carbon-based dual-metal site catalysts for energy applications. Nano Res. 2023, 16, 6477–6506.
Crossref Google Scholar
[6]

Chen, Y. X.; Lavacchi, A.; Miller, H. A.; Bevilacqua, M.; Filippi, J.; Innocenti, M.; Marchionni, A.; Oberhauser, W.; Wang, L.; Vizza, F. Nanotechnology makes biomass electrolysis more energy efficient than water electrolysis. Nat. Commun. 2014, 5, 4036.
Crossref Google Scholar
[7]

Wang, T. J.; Li, F. M.; Huang, H.; Yin, S. W.; Chen, P.; Jin, P. J.; Chen, Y. Porous Pd-PdO nanotubes for methanol electrooxidation. Adv. Funct. Mater. 2020, 30, 2000534.
Crossref Google Scholar
[8]

Liu, J. F.; Wang, Q. X.; Li, T.; Wang, Y.; Li, H. M.; Cabot, A. PdMoSb trimetallene as high-performance alcohol oxidation electrocatalyst. Nano Res. 2023, 16, 2041–2048.
Crossref Google Scholar
[9]
Li, J. Y.; Xu, X. J.; Hou, X. B.; Zhang, S. C.; Su, G.; Tian, W. Q.; Wang, H. L.; Huang, M. H.; Toghan, A. Interface engineering of NiSe2 nanowrinkles/Ni5P4 nanorods for boosting urea oxidation reaction at large current densities. Nano Res., in press, https://doi.org/10.1007/s12274-023-5575-4.
[10]

Wu, X. H.; Wang, Y.; Wu, Z. S. Design principle of electrocatalysts for the electrooxidation of organics. Chem 2022, 8, 2594–2629.
Crossref Google Scholar
[11]

Han, X. T.; Sheng, H. Y.; Yu, C.; Walker, T. W.; Huber, G. W.; Qiu, J. S.; Jin, S. Electrocatalytic oxidation of glycerol to formic acid by CuCo2O4 spinel oxide nanostructure catalysts. ACS Catal. 2020, 10, 6741–6752.
Crossref Google Scholar
[12]

Yu, X. W.; Araujo, R. B.; Qiu, Z.; dos Santos, E. C.; Anil, A.; Cornell, A.; Pettersson, L. G. M.; Johnsson, M. Hydrogen evolution linked to selective oxidation of glycerol over CoMoO4—A theoretically predicted catalyst. Adv. Energy Mater. 2022, 12, 2103750.
Crossref Google Scholar
[13]

Eppinger, J.; Huang, K. W. Formic acid as a hydrogen energy carrier. Acs Energy Lett. 2017, 2, 188–195.
Crossref Google Scholar
[14]

Grasemann, M.; Laurenczy, G. Formic acid as a hydrogen source-recent developments and future trends. Energy Environ. Sci. 2012, 5, 8171–8181.
Crossref Google Scholar
[15]

Dodekatos, G.; Schünemann, S.; Tüysüz, H. Recent advances in thermo-, photo-, and electrocatalytic glycerol oxidation. ACS Catal. 2018, 8, 6301–6333.
Crossref Google Scholar
[16]

Oh, L. S.; Park, M.; Park, Y. S.; Kim, Y.; Yoon, W.; Hwang, J.; Lim, E.; Park, J. H.; Choi, S. M.; Seo, M. H. et al. How to change the reaction chemistry on nonprecious metal oxide nanostructure materials for electrocatalytic oxidation of biomass-derived glycerol to renewable chemicals? Adv. Mater. 2023, 35, 2203285.
Crossref Google Scholar
[17]

Pagliaro, M.; Ciriminna, R.; Kimura, H.; Rossi, M.; Della Pina, C. From glycerol to value-added products. Angew. Chem., Int. Ed. 2007, 46, 4434–4440.
Crossref Google Scholar
[18]

Ting, N. H.; Nguyen, T. X.; Lee, C. H.; Chen, Y. C.; Yeh, C. H.; Chen, H. Y. T.; Ting, J. M. Composition-controlled high entropy metal glycerate as high-performance electrocatalyst for oxygen evolution reaction. Appl. Mater. Today. 2022, 27, 101398.
Crossref Google Scholar
[19]

He, Z. Y.; Hwang, J.; Gong, Z. H.; Zhou, M. Z.; Zhang, N.; Kang, X. W.; Han, J. W.; Chen, Y. Promoting biomass electrooxidation via modulating proton and oxygen anion deintercalation in hydroxide. Nat. Commun. 2022, 13, 3777.
Crossref Google Scholar
[20]

Zhang, L. J.; Cai, W. W.; Bao, N. Z.; Yang, H. Implanting an electron donor to enlarge the d-p hybridization of high-entropy (oxy)hydroxide: A novel design to boost oxygen evolution. Adv. Mater. 2022, 34, 2110511.
Crossref Google Scholar
[21]

Lei, Y. T.; Zhang, L. L.; Xu, W. J.; Xiong, C. L.; Chen, W. X.; Xiang, X.; Zhang, B.; Shang, H. S. Carbon-supported high-entropy Co-Zn-Cd-Cu-Mn sulfide nanoarrays promise high-performance overall water splitting. Nano Res. 2022, 15, 6054–606.
Crossref Google Scholar
[22]

Liu, X.; Fang, Z. Y.; Teng, X.; Niu, Y. L.; Gong, S. Q.; Chen, W.; Meyer, T. J.; Chen, Z. F. Paired formate and H2 productions via efficient bifunctional Ni-Mo nitride nanowire electrocatalysts. J. Energy Chem. 2022, 72, 432–441.
Crossref Google Scholar
[23]

Bai, J.; Huang, H.; Li, F. M.; Zhao, Y.; Chen, P.; Jin, P. J.; Li, S. N.; Yao, H. C.; Zeng, J. H.; Chen, Y. Glycerol oxidation assisted electrocatalytic nitrogen reduction: Ammonia and glyceraldehyde co-production on bimetallic RhCu ultrathin nanoflake nanoaggregates. J. Mater. Chem. A 2019, 7, 21149–21156.
Crossref Google Scholar
[24]

Zheng, D. D.; Li, J. W.; Ci, S. Q.; Cai, P. W.; Ding, Y. C.; Zhang, M. T.; Wen, Z. H. Three-birds-with-one-stone electrolysis for energy-efficiency production of gluconate and hydrogen. Appl. Catal. B: Environ. 2020, 277, 119178.
Crossref Google Scholar
[25]

Fan, L. F.; Ji, Y. X.; Wang, G. X.; Zhang, Z. F.; Yi, L. C.; Chen, K.; Liu, X.; Wen, Z. H. Bifunctional Mn-doped CoSe2 nanonetworks electrode for hybrid alkali/acid electrolytic H2 generation and glycerol upgrading. J. Energy Chem. 2022, 72, 424–431.
Crossref Google Scholar
[26]

Zhou, J.; Dou, Y. B.; He, T.; Zhou, A. W.; Kong, X. J.; Wu, X. Q.; Liu, T. X.; Li, J. R. Revealing the effect of anion-tuning in bimetallic chalcogenides on electrocatalytic overall water splitting. Nano Res. 2021, 14, 4548–4555.
Crossref Google Scholar
[27]

Ma, Y. J.; Ma, Y.; Wang, Q. S.; Schweidler, S.; Botros, M.; Fu, T. T.; Hahn, H.; Brezesinski, T.; Breitung, B. High-entropy energy materials: Challenges and new opportunities. Energy Environ. Sci. 2021, 14, 2883–2905.
Crossref Google Scholar
[28]

Jiang, B.; Bridges, C. A.; Unocic, R. R.; Pitike, K. C.; Cooper, V. R.; Zhang, Y. P.; Lin, D. Y.; Page, K. Probing the local site disorder and distortion in pyrochlore high-entropy oxides. J. Am. Chem. Soc. 2021, 143, 4193–4204.
Crossref Google Scholar
[29]

Lee, C.; Song, G.; Gao, M. C.; Feng, R.; Chen, P. Y.; Brechtl, J.; Chen, Y.; An, K.; Guo, W.; Poplawsky, J. D. et al. Lattice distortion in a strong and ductile refractory high-entropy alloy. Acta Mater. 2018, 160, 158–172.
Crossref Google Scholar
[30]

Yu, C. L.; Wu, Z.; Liu, R. Y.; Dionysiou, D. D.; Yang, K.; Wang, C. Y.; Liu, H. Novel fluorinated Bi2MoO6 nanocrystals for efficient photocatalytic removal of water organic pollutants under different light source illumination. Appl. Catal. B: Environ. 2017, 209, 1–11.
Crossref Google Scholar
[31]

Xia, C.; Liang, H. F.; Zhu, J. J.; Schwingenschlögl, U.; Alshareef, H. N. Active edge sites engineering in nickel cobalt selenide solid solutions for highly efficient hydrogen evolution. Adv. Energy Mater. 2017, 7, 1602089.
Crossref Google Scholar
[32]

Zhu, W. X.; Wang, J.; Zhang, W. T.; Hu, N.; Wang, J.; Huang, L. J.; Wang, R.; Suo, Y. R.; Wang, J. L. Monolithic copper selenide submicron particulate film/copper foam anode catalyst for ultrasensitive electrochemical glucose sensing in human blood serum. J. Mater. Chem. B 2018, 6, 718–724.
Crossref Google Scholar
[33]

Feng, H.; Li, J. H.; Liu, Y. Q.; Xu, Z. F.; Cui, Y.; Liu, M. Q.; Liu, X.; He, L. Z.; Jiang, J. B.; Qian, D. Cubic MnSe2 nanoparticles dispersed on multi-walled carbon nanotubes: A robust electrochemical sensing platform for chloramphenicol. J. Electroanal. Chem. 2022, 922, 116755.
Crossref Google Scholar
[34]

Han, Z. S.; Kong, F. J.; Zheng, J. H.; Chen, J. Y.; Tao, S.; Qian, B. MnSe nanoparticles encapsulated into N-doped carbon fibers with a binder-free and free-standing structure for lithium ion batteries. Ceram. Int. 2021, 47, 1429–1438.
Crossref Google Scholar
[35]

Hu, L.; He, L. Q.; Wang, X.; Shang, C. Q.; Zhou, G. F. MnSe embedded in carbon nanofibers as advanced anode material for sodium ion batteries. Nanotechnology 2020, 31, 335402.
Crossref Google Scholar
[36]

Javed, M. S.; Shah, S. S. A.; Hussain, S.; Tan, S. Z.; Mai, W. J. Mesoporous manganese-selenide microflowers with enhanced electrochemical performance as a flexible symmetric 1.8 V supercapacitor. Chem. Eng. J. 2020, 382, 122814.
Crossref Google Scholar
[37]

Abdallah, W. A.; Nelson, A. E. Characterization of MoSe2 (0001) and ion-sputtered MoSe2 by XPS. J. Mater Sci. 2005, 40, 2679–2681.
Crossref Google Scholar
[38]

Choffel, M. A.; Gannon, R. N.; Göhler, F.; Miller, A. M.; Medlin, D. L.; Seyller, T.; Johnson, D. C. Synthesis and electrical properties of a new compound (BiSe)0.97(Bi2Se3)1.26(BiSe)0.97(MoSe2) containing metallic 1T-MoSe2. Chem. Mater. 2021, 33, 6403–6411.
Crossref Google Scholar
[39]

Hadland, E. C.; Göhler, F.; Mitchson, G.; Fender, S. S.; Schmidt, C.; Zahn, D. R. T.; Seyller, T.; Johnson, D. C. Synthesis and properties of (BiSe)0.97MoSe2: A heterostructure containing both 2H-MoSe2 and 1T-MoSe2. Chem. Mater. 2019, 31, 5824–5831.
Crossref Google Scholar
[40]

Zhou, Y. F.; Shen, Y.; Xi, J. Y. Seed-mediated synthesis of PtxAuy@Ag electrocatalysts for the selective oxidation of glycerol. Appl. Catal. B: Environ. 2019, 245, 604–612.
Crossref Google Scholar
[41]

Gomes, J. F.; Tremiliosi-Filho, G. Spectroscopic studies of the glycerol electro-oxidation on polycrystalline Au and Pt surfaces in acidic and alkaline media. Electrocatalysis 2011, 2, 96–105.
Crossref Google Scholar
[42]

Houache, M. S. E.; Hughes, K.; Ahmed, A.; Safari, R.; Liu, H. S.; Botton, G. A.; Baranova, E. A. Electrochemical valorization of glycerol on Ni-rich bimetallic NiPd nanoparticles: Insight into product selectivity using in situ polarization modulation infrared-reflection absorption spectroscopy. ACS Sustain. Chem. Eng. 2019, 7, 14425–14434.
Crossref Google Scholar
[43]

Houache, M. S. E.; Safari, R.; Nwabara, U. O.; Rafaïdeen, T.; Botton, G. A.; Kenis, P. J. A.; Baranton, S.; Coutanceau, C.; Baranova, E. A. Selective electrooxidation of glycerol to formic acid over carbon supported Ni1−xMx (M = Bi, Pd, and Au) nano-catalysts and coelectrolysis of CO2. ACS Appl. Energy Mater. 2020, 3, 8725–8738.
Crossref Google Scholar
[44]

Qiao, H. Y.; Wang, X. Z.; Dong, Q.; Zheng, H. K.; Chen, G.; Hong, M.; Yang, C. P.; Wu, M. L.; He, K.; Hu, L. B. A high-entropy phosphate catalyst for oxygen evolution reaction. Nano Energy 2021, 86, 106029.
Crossref Google Scholar
[45]

Jeong, I.; Cho, K.; Yun, S.; Shin, J.; Kim, J.; Kim, G. T.; Lee, T.; Chung, S. Tailoring the electrical characteristics of MoS2 FETs through controllable surface charge transfer doping using selective inkjet printing. ACS Nano 2022, 16, 6215–6223.
Crossref Google Scholar
[46]

Tanaka, T.; Sueishi, T.; Saito, K.; Guo, Q. X.; Nishio, M.; Yu, K. M.; Walukiewicz, W. Existence and removal of Cu2Se second phase in coevaporated Cu2ZnSnSe4 thin films. J. Appl. Phys. 2012, 111, 053522.
Crossref Google Scholar
[47]

Beak, G. Y.; Jeon, C. W. XPS and Raman study of slope-polished Cu(In,Ga)Se2 thin films. Electron. Mater. Lett. 2016, 12, 399–403.
Crossref Google Scholar
[48]

Zhang, L.; Zhao, S. L.; Li, Y. F.; Lan, Y. Q.; Han, M.; Dai, Z. H.; Bao, J. C. Monoclinic copper(I) selenide nanocrystals and copper(I) selenide/palladium heterostructures: Synthesis, characterization, and surface-enhanced Raman scattering performance. Eur. J. Inorg. Chem. 2015, 2015, 2229–2236.
Crossref Google Scholar
[49]

Qin, R.; Wang, P. Y.; Li, Z. L.; Zhu, J. X.; Cao, F.; Xu, H. W.; Ma, Q. L.; Zhang, J. Y.; Yu, J.; Mu, S. C. Ru-incorporated nickel diselenide nanosheet arrays with accelerated adsorption kinetics toward overall water splitting. Small 2022, 18, 2105305.
Crossref Google Scholar
[50]

Chen, Z.; Cai, L.; Yang, X. F.; Kronawitter, C.; Guo, L. J.; Shen, S. H.; Koel, B. E. Reversible structural evolution of NiCoOxHy during the oxygen evolution reaction and identification of the catalytically active phase. ACS Catal. 2018, 8, 1238–1247.
Crossref Google Scholar
[51]

Diaz-Morales, O.; Ferrus-Suspedra, D.; Koper, M. T. M. The importance of nickel oxyhydroxide deprotonation on its activity towards electrochemical water oxidation. Chem Sci. 2016, 7, 2639–2645.
Crossref Google Scholar
[52]

Chen, D. C.; Xiong, X. H.; Zhao, B. T.; Mahmoud, M. A.; El-Sayed, M. A.; Liu, M. L. Probing structural evolution and charge storage mechanism of NiO2Hx electrode materials using in operando resonance Raman spectroscopy. Adv. Sci. 2016, 3, 1500433.
Crossref Google Scholar
[53]

Zhang, L. L.; Wang, Z. P.; Zhang, J. T.; Lin, Z. P.; Zhang, Q. H.; Zhong, W. W.; Wu, G. F. High activity and stability in Ni2P/(Co,Ni)OOH heterointerface with a multiple-hierarchy structure for alkaline hydrogen evolution reaction. Nano Res. 2023, 16, 6552–6559.
Crossref Google Scholar
[54]

Yu, Y. N.; Xia, F. J.; Wang, C. J.; Wu, J. S.; Fu, X. B.; Ma, D. S.; Lin, B. C.; Wang, J. A.; Yue, Q.; Kang, Y. J. High-entropy alloy nanoparticles as a promising electrocatalyst to enhance activity and durability for oxygen reduction. Nano Res. 2022, 15, 7868–7876.
Crossref Google Scholar
[55]

Liu, Y. W.; Hua, X. M.; Xiao, C.; Zhou, T. F.; Huang, P. C.; Guo, Z. P.; Pan, B. C.; Xie, Y. Heterogeneous spin states in ultrathin nanosheets induce subtle lattice distortion to trigger efficient hydrogen evolution. J. Am. Chem. Soc. 2016, 138, 5087–5092.
Crossref Google Scholar
[56]

Cheng, B. Y.; Lou, H. B.; Sarkar, A.; Zeng, Z. D.; Zhang, F.; Chen, X. H.; Tan, L. J.; Prakapenka, V.; Greenberg, E.; Wen, J. G. et al. Pressure-induced tuning of lattice distortion in a high-entropy oxide. Commun. Chem. 2019, 2, 114.
Crossref Google Scholar
[57]

Ding, Y. C.; Cai, P. W.; Wen, Z. H. Electrochemical neutralization energy: From concept to devices. Chem. Soc. Rev. 2021, 50, 1495–1511.
Crossref Google Scholar
[58]

Miao, X. B.; Zhang, L. F.; Wu, L.; Hu, Z. P.; Shi, L.; Zhou, S. M. Quadruple perovskite ruthenate as a highly efficient catalyst for acidic water oxidation. Nat. Commun. 2019, 10, 3809.
Crossref Google Scholar
Nano Research
Volume 16 Issue 8,
August 2023
Pages 10832-10839
DOI: 10.1007/s12274-023-5842-4
Cite this article:
Yao H, Wang Y, Zheng Y, et al. High-entropy selenides: A new platform for highly selective oxidation of glycerol to formate and energy-saving hydrogen evolution in alkali-acid hybrid electrolytic cell. Nano Research, 2023, 16(8): 10832-10839. https://doi.org/10.1007/s12274-023-5842-4
Topics:
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Received: 13 April 2023
Revised: 11 May 2023
Accepted: 12 May 2023
Published: 13 June 2023
© Tsinghua University Press 2023
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