二氧化碳电化学还原(CO_(2)RR)制备碳氢化合物是一项极具应用前景的技术.该技术不仅可以有效减少二氧化碳在大气中的积累,还可以储存可再生能源.然而,由于现有的CO_(2)RR电催化剂的活性和法拉第效率较低,难以实现大规模应用.离子液体电...二氧化碳电化学还原(CO_(2)RR)制备碳氢化合物是一项极具应用前景的技术.该技术不仅可以有效减少二氧化碳在大气中的积累,还可以储存可再生能源.然而,由于现有的CO_(2)RR电催化剂的活性和法拉第效率较低,难以实现大规模应用.离子液体电解质可以有效提高CO_(2)RR的选择性,但成本太高,将离子液体固定在异相电催化剂的孔洞中可以大幅减少离子液体的用量.本文设计了一种混合HKUST-1金属-有机框架(MOF)-氟化咪唑基室温离子液体的电催化剂,将1-丁基-3-甲基咪唑六氟磷酸盐([BMIM][PF6])和1-乙基-3-甲基咪唑四氟硼酸盐([EMIM][BF_(4)])室温离子液体在真空氛围中被负载到水热合成的HKUST-1微粒孔隙中形成复合催化剂,该催化剂可以选择性地将CO_(2)还原为CH_(4).X射线光电子能谱(XPS)结果表明,室温离子液体和HKUST-1 MOF的Cu中心之间存在明显的电子相互作用,其中低氧化态的Cu比例较高.X射线衍射(XRD)和透射电子显微镜(TEM)结果表明,室温离子液体的负载没有显著改变MOF的晶体结构及其形态.与原始的HKUST-1电催化剂相比,HKUST-1/[BMIM][PF_(6)]混合催化剂的CH_(4)法拉第效率(FE)明显提高.在‒1.13 V vs.RHE时,最大CH_(4) FE和分电流密度分别为65.5%和11.5 mA cm^(-2).同时,混合催化剂的析氢反应(HER)活性显著降低,在‒1.09 V vs.RHE时H_(2) FE只有6.8%.稳定性测试结果表明,CH_(4) FE可以稳定保持在50%以上.由于在HKUST-1/[BMIM]和HKUST-1/[EMIM][BF_(4)]混合催化剂的测试中观察到了类似的促进CH_(4)和抑制HER的趋势,可以推断室温离子液体的疏水性在提高CO_(2)RR选择性方面只起到次要作用.电解后催化剂表面形成纳米级铜簇,可能是真正的活性位点.基于实验结果,本文还模拟了表面吸附了[BMIM][PF_(6)]分子的Cu(110)晶面,密度泛函理论(DFT)计算结果表明,在表面存在室温离子液体的情况下,Cu的分态密度(PDOS)峰正移,表明Cu可以与CO_(2)RR的反应中间体形成更强的键.HER的自由能图结果表明,室温离子液体的存在明显增强了H的吸附,从而通过增加*H的脱附能垒来阻碍析氢.此外,对CO_(2)到CH_(4)反应路径的计算表明,室温离子液体的存在降低了CO_(2)-CH_(4)的热力学能垒.展开更多
Ammonia electrooxidation reaction involving multistep electron-proton transfer is a significant reaction for fuel cells,hydrogen production and understanding nitrogen cycle.Platinum has been established as the best el...Ammonia electrooxidation reaction involving multistep electron-proton transfer is a significant reaction for fuel cells,hydrogen production and understanding nitrogen cycle.Platinum has been established as the best electrocatalyst for ammonia oxidation in aqueous alkaline media.In this study,Pt/nitrogen-doped graphene(NDG)and Pt/tungsten monocarbide(WC)/NDG are synthesized by a wet chemistry method and their ammonia oxidation activities are compared to commercial Pt/C.Pt/NDG exhibits a specific activity of 0.472 mA·cm^(-2),which is 44%higher than commercial Pt/C,thus establishing NDG as a more effective support than carbon black.Moreover,it is demonstrated that WC as a support also impacts the activity with further 30%increase in comparison to NDG.Surface modification with Ir resulted in the best electro-catalytic activity with Pt-IrAVC/NDG having almost thrice the current density of commercial Pt/C.This work adds insights regarding the role of NDG and WC as efficient supports along with significant impact of Ir surface modification.展开更多
文摘二氧化碳电化学还原(CO_(2)RR)制备碳氢化合物是一项极具应用前景的技术.该技术不仅可以有效减少二氧化碳在大气中的积累,还可以储存可再生能源.然而,由于现有的CO_(2)RR电催化剂的活性和法拉第效率较低,难以实现大规模应用.离子液体电解质可以有效提高CO_(2)RR的选择性,但成本太高,将离子液体固定在异相电催化剂的孔洞中可以大幅减少离子液体的用量.本文设计了一种混合HKUST-1金属-有机框架(MOF)-氟化咪唑基室温离子液体的电催化剂,将1-丁基-3-甲基咪唑六氟磷酸盐([BMIM][PF6])和1-乙基-3-甲基咪唑四氟硼酸盐([EMIM][BF_(4)])室温离子液体在真空氛围中被负载到水热合成的HKUST-1微粒孔隙中形成复合催化剂,该催化剂可以选择性地将CO_(2)还原为CH_(4).X射线光电子能谱(XPS)结果表明,室温离子液体和HKUST-1 MOF的Cu中心之间存在明显的电子相互作用,其中低氧化态的Cu比例较高.X射线衍射(XRD)和透射电子显微镜(TEM)结果表明,室温离子液体的负载没有显著改变MOF的晶体结构及其形态.与原始的HKUST-1电催化剂相比,HKUST-1/[BMIM][PF_(6)]混合催化剂的CH_(4)法拉第效率(FE)明显提高.在‒1.13 V vs.RHE时,最大CH_(4) FE和分电流密度分别为65.5%和11.5 mA cm^(-2).同时,混合催化剂的析氢反应(HER)活性显著降低,在‒1.09 V vs.RHE时H_(2) FE只有6.8%.稳定性测试结果表明,CH_(4) FE可以稳定保持在50%以上.由于在HKUST-1/[BMIM]和HKUST-1/[EMIM][BF_(4)]混合催化剂的测试中观察到了类似的促进CH_(4)和抑制HER的趋势,可以推断室温离子液体的疏水性在提高CO_(2)RR选择性方面只起到次要作用.电解后催化剂表面形成纳米级铜簇,可能是真正的活性位点.基于实验结果,本文还模拟了表面吸附了[BMIM][PF_(6)]分子的Cu(110)晶面,密度泛函理论(DFT)计算结果表明,在表面存在室温离子液体的情况下,Cu的分态密度(PDOS)峰正移,表明Cu可以与CO_(2)RR的反应中间体形成更强的键.HER的自由能图结果表明,室温离子液体的存在明显增强了H的吸附,从而通过增加*H的脱附能垒来阻碍析氢.此外,对CO_(2)到CH_(4)反应路径的计算表明,室温离子液体的存在降低了CO_(2)-CH_(4)的热力学能垒.
基金the Southern Marine Sciencc and Engineering Guangdong Laboratory(Guangzhou)(Grant No.SMSEGL20SC01)Innovation and Technology Commission(Grant No.ITC-CNERC14EG03)of the Hong Kong Special Administrative Regionstartup funding of Hong Kong University of Science and Technology.
文摘Ammonia electrooxidation reaction involving multistep electron-proton transfer is a significant reaction for fuel cells,hydrogen production and understanding nitrogen cycle.Platinum has been established as the best electrocatalyst for ammonia oxidation in aqueous alkaline media.In this study,Pt/nitrogen-doped graphene(NDG)and Pt/tungsten monocarbide(WC)/NDG are synthesized by a wet chemistry method and their ammonia oxidation activities are compared to commercial Pt/C.Pt/NDG exhibits a specific activity of 0.472 mA·cm^(-2),which is 44%higher than commercial Pt/C,thus establishing NDG as a more effective support than carbon black.Moreover,it is demonstrated that WC as a support also impacts the activity with further 30%increase in comparison to NDG.Surface modification with Ir resulted in the best electro-catalytic activity with Pt-IrAVC/NDG having almost thrice the current density of commercial Pt/C.This work adds insights regarding the role of NDG and WC as efficient supports along with significant impact of Ir surface modification.
