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...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。展开更多
Construction of highly active and stable bifunctional catalysts for 5-hydroxymethylfurfural oxidation reaction(HMFOR)and hydrogen evolution reaction(HER)is meaningful but remains a challenge.Herein,the NiCo–Mo_(2)N h...Construction of highly active and stable bifunctional catalysts for 5-hydroxymethylfurfural oxidation reaction(HMFOR)and hydrogen evolution reaction(HER)is meaningful but remains a challenge.Herein,the NiCo–Mo_(2)N heterostructure nanosheets catalyst with excellent HMFOR/HER performance is obtained by a simple hydrothermal and calcination method.The heterogeneous interface between NiCo and Mo_(2)N induces electron redistribution,regulating the electronic structure of the catalyst and thus optimizing the adsorption/desorption behavior of HMFOR/HER intermediates.Consequently,NiCo–Mo_(2)N/NF exhibits superior catalytic activity with a potential of 1.14 V_(RHE)/−17 mV_(RHE)(HMFOR/HER)at±10 mA cm^(−2),and the HMF conversion rate,FDCA yield,and Faradaic efficiency(FE)are∼100%,99.98%,and 98.65%,respectively.Besides,it only requires a low voltage of 1.36 V to achieve 100 mA cm^(−2)for HMFOR-assisted H2 production.This study provides a strategy for the development of efficient bifunctional catalysts for sustainable production of high value-added products and hydrogen.展开更多
文摘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。
基金supported by the National Natural Science Foundation of China(22162004)the Natural Science Foundation of Guangxi Province(2022JJD120011).
文摘Construction of highly active and stable bifunctional catalysts for 5-hydroxymethylfurfural oxidation reaction(HMFOR)and hydrogen evolution reaction(HER)is meaningful but remains a challenge.Herein,the NiCo–Mo_(2)N heterostructure nanosheets catalyst with excellent HMFOR/HER performance is obtained by a simple hydrothermal and calcination method.The heterogeneous interface between NiCo and Mo_(2)N induces electron redistribution,regulating the electronic structure of the catalyst and thus optimizing the adsorption/desorption behavior of HMFOR/HER intermediates.Consequently,NiCo–Mo_(2)N/NF exhibits superior catalytic activity with a potential of 1.14 V_(RHE)/−17 mV_(RHE)(HMFOR/HER)at±10 mA cm^(−2),and the HMF conversion rate,FDCA yield,and Faradaic efficiency(FE)are∼100%,99.98%,and 98.65%,respectively.Besides,it only requires a low voltage of 1.36 V to achieve 100 mA cm^(−2)for HMFOR-assisted H2 production.This study provides a strategy for the development of efficient bifunctional catalysts for sustainable production of high value-added products and hydrogen.
