Mesoporous Palladium⁃Boron Alloy Nanocatalysts： Synthesis and Performance in Methanol Oxidation Electrocatalysis

doi:10.19894/j.issn.1000-0518.210449

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (4): 673-684.DOI: 10.19894/j.issn.1000-0518.210449

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Mesoporous Palladium⁃Boron Alloy Nanocatalysts： Synthesis and Performance in Methanol Oxidation Electrocatalysis

Li-Zhi SUN, Hao LYU, Xiao-Wen MIN, Ben LIU()

Key Laboratory of Green Chemistry and Technology of Ministry of Education，College of Chemistry，Sichuan University，Chengdu 610064，China

Received:2021-09-02 Accepted:2021-12-29 Published:2022-04-01 Online:2022-04-19
Contact: Ben LIU
About author:ben.liu@scu.edu.cn
Supported by:
the Open Project of State Key Laboratory of Supramolecular Structure and Materials(sklssm2021011);the Fundamental Research Funds for the Central Universities

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Abstract

Abstract:

Alloying is able to adjust physical and chemical properties of noble metal-based nanocatalysts， thus significantly improving their electrocatalytic performance. Although alloying has made many achievements in the past two decades， it still needs in-depth research and understanding to make full use of the advantages of nano-alloys. In this study， we reported a one-step solution-phase synthesis method to co-alloy metalloid boron （B） in palladium-based mesoporous nanocatalysts and further demonstrated their high electrochemical methanol oxidation reaction （MOR） performance in alkaline media. The best PdCuB mesoporous nanocatalyst shows excellent electrochemical MOR activity （2.48 A mg_Pd^-1） and stability. The catalytic mechanism studies shows that B atom not only changes the electronic structure of Pd sites which directly weakens the adsorption strength of CO-based intermediates but also promotes the adsorption of OH^－ which optimizes the oxidation of CO-based intermediates （the rete-determining step）. Such a synergy remarkably improves the MOR kinetics and enhances its catalytic performance accordingly. Meanwhile， interstitially inserting metallic B atoms and structural mesoporosity also inhibites the physical Ostwald ripening process and thus stabilizes the catalyst.

Key words: Alloy, Mesoporosity, Methanol oxidation, Catalytic kinetics, Electrocatalysis

CLC Number:

O643

Li-Zhi SUN, Hao LYU, Xiao-Wen MIN, Ben LIU. Mesoporous Palladium⁃Boron Alloy Nanocatalysts： Synthesis and Performance in Methanol Oxidation Electrocatalysis[J]. Chinese Journal of Applied Chemistry, 2022, 39(4): 673-684.

Figures/Tables 9

Fig.1 Schematic illustration of the synthesis of PdCuB MNSs

Fig.2 Structural and compositional characterizations of PdCuB MNSs

Fig.3 （A） XRD and （B） zoom-in XRD patterns in the range of 35~50（°） of （a） Pd MNSs，（b） PdB MNSs，（c） PdCu MNSs and （d） PdCuB MNSs

Fig.4 High-resolution （A） Pd3d，（B） B1s and （C） Cu2p XPS spectra of Pd MNSs， PdB MNSs， PdCu MNSs and PdCuB MNSs

Fig.5 Electrochemical performance in KOH. （A） CV curves and （B） summarized ECSAs of Pd/C， Pd MNSs， PdB MNSs， PdCu MNSs and PdCuB MNSs. （C） CV curves of PdCuB MNSs collected with different scan rates. （D） Relationships between scan rates and peak specific currents of Pd/C， Pd MNSs， PdB MNSs， PdCu MNSs and PdCuB MNSs

Fig.6 Electrochemical CO stripping curves of Pd/C， Pd MNSs， PdB MNSs， PdCu MNSs and PdCuB MNSs

Fig.7 Electrochemical MOR performance. （A） CV curves，（B） summarized mass activities，（C） Eavalues， and （D） Nyquist plots of Pd/C， Pd MNSs， PdB MNSs， PdCu MNSs and PdCuB MNSs

Fig.8 （A） The relationship between KOH concentrations and MOR activities of Pd/C， Pd MNSs， PdB MNSs， PdCu MNSs， and PdCuB MNSs；（B） The relationship between methanol concentrations and MOR activities of Pd/C， Pd MNSs， PdB MNSs， PdCu MNSs and PdCuB MNSs

Fig.9 （A） CV curves and （B） summarized mass activities of PdCuB MNSs and PdCu MNSs during CV scans for 2500 cycles. （C） MOR i-t curves of PdCuB MNSs and Pd/C with ten test cycles

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Mesoporous Palladium⁃Boron Alloy Nanocatalysts： Synthesis and Performance in Methanol Oxidation Electrocatalysis

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