摘要
生物质作为一种可再生的有机碳源,可满足人类对能源和化学品的巨大需求。其中,5-羟甲基糠醛(HMF)是最具应用潜力的生物质衍生平台分子之一,其氧化产物2,5-呋喃二甲酸(FDCA)有望替代对苯二甲酸(PTA)用于合成生物基降解塑料。由于反应条件温和、速率快和选择性高,电催化氧化HMF已成为制备FDCA非常有前景的绿色方法。此外,阳极电氧化HMF反应的理论电位(HMFOR,0.3 V vs.RHE)远低于析氧反应(OER,1.23 V vs.RHE),将其与阴极析氢反应(HER)耦合,有望在生产高附加值FDCA的同时降低产氢电位。然而,构建高效稳定的双功能催化剂用于HMFOR辅助制氢仍然具有挑战性。本文通过水热和高温煅烧的方法在泡沫镍上生长Co掺杂的Ni-Mo-O多孔纳米棒(Co-NiMoO/NF)用于HMFOR(E10/100=1.31/1.37 V vs.RHE)和HER(E−10/−100=−35/−123 mV vs.RHE),均表现出良好的活性和稳定性。对于HMFOR,Co-NiMoO/NF可以在1.36 V vs.RHE的恒电位下连续运行40个循环并保持较高的FDCA选择性(~99.2%)和法拉第效率(~95.7%)。对于HER,Co-NiMoO/NF可以在−200 mA∙cm^(−2)的电流密度下稳定运行50 h。作为双功能电极用于全HMF分解时,仅需1.48 V可达到50 mA∙cm^(−2),较全水解降低了290 mV,证明了Co-NiMoO/NF电氧化HMF辅助制氢大幅降低能耗的可行性。特别是,双电极体系能在1.45 V恒电位的驱动下,高效稳定地工作10个循环,并保持较高的FDCA选择性(~97.6%),表现出较好的应用潜力。Co-NiMoO/NF的良好催化性能可归因于Co的引入优化了Ni-Mo-O的电子结构和对反应物的吸附行为,从而提高了催化剂的本征活性和稳定性。同时,多孔纳米棒有助于底物分子和气泡在其表面的传输和脱附,进而提高了HMFOR/HER的反应动力学。这项工作有望为HMFOR和HER的高效稳定双功能催化剂的设计提供有益见解。
Fossil fuel depletion and environmental deterioration have created an urgent need to develop renewable and clean energy.Biomass,a sustainable organic carbon source,can meet the huge demand for energy and chemicals.Among them,5-hydroxymethylfurfural(HMF)is an important biomass-derived platform molecule,which can be converted into various high-value chemicals.One of its oxidation products,2,5-furandicarboxylic acid(FDCA),is expected to replace terephthalic acid as a raw material for the synthesis of bio-based degradable plastics.The electrooxidation of HMF emerges as a promising green route for preparing FDCA due to its advantages of mild conditions,fast reaction rate,and high selectivity.The theoretical potential of the HMF electrooxidation reaction(HMFOR,0.3 V vs.reversible hydrogen electrode,RHE)is also lower than that of the oxygen evolution reaction(OER,1.23 V vs.RHE).Coupling anodic HMFOR with cathodic hydrogen evolution reaction(HER)is expected to simultaneously produce valuable FDCA and reduce the cell voltage of hydrogen(H2)evolution.However,the construction of efficient and stable bifunctional catalysts for HMFOR-assisted H2 production is still challenging.In this study,Co-doped Ni-Mo-O porous nanorods grown on a nickel foam(Co-NiMoO/NF)is prepared by simple hydrothermal and calcination methods for both HMFOR and HER.Results of electrocatalytic studies indicate that Co-NiMoO/NF exhibits enhanced performance for HMFOR(E10/100=1.31/1.37 V vs.RHE)and HER(E−10/−100=−35/−123 mV vs.RHE)and shows durable HMFOR/HER stability.In particular,Co-NiMoO/NF maintains high FDCA selectivity(~99.2%)and Faradaic efficiency(~95.7%)for 40 successive cycles at 1.36 V vs.RHE for HMFOR.Conversely,Co-NiMoO/NF maintains stable operation at−200 mA∙cm^(−2) for 50 h with no significant activity attenuation for HER.When coupled as a bifunctional electrode for overall HMF splitting,Co-NiMoO/NF reaches an electric flux of 50 mA∙cm^(−2) at 1.48 V,which is 290 mV lower than that of the overall water splitting.This confir
作者
郑书逸
吴佳
王可
胡梦晨
文欢
尹诗斌
Shuyi Zheng;Jia Wu;Ke Wang;Mengchen Hu;Huan Wen;Shibin Yin(Guangxi Key Laboratory of Electrochemical Energy Materials,College of Chemistry and Chemical Engineering,Guangxi University,Nanning 530004,China.)
出处
《物理化学学报》
SCIE
CAS
CSCD
北大核心
2023年第12期113-123,共11页
Acta Physico-Chimica Sinica
基金
国家自然科学基金(22162004)
广西自然科学基金(2022JJD120011)资助项目。
关键词
5-羟甲基糠醛氧化反应
析氢反应
催化剂
多孔结构
电子结构
5-Hydroxymethylfurfural oxidation reaction
Hydrogen evolution reaction
Catalyst
Porous structure
Electronic structure
