质子交换膜燃料电池(PEMFCs)将化学燃料转化为电能,具有能量转换效率高、清洁、零排放等特点,被认为是未来重要的能源利用装置.与阳极发生的氢氧化反应相比,阴极发生的氧还原反应(ORR)是动力学缓慢的过程,严重阻碍了燃料电池的广泛应用...质子交换膜燃料电池(PEMFCs)将化学燃料转化为电能,具有能量转换效率高、清洁、零排放等特点,被认为是未来重要的能源利用装置.与阳极发生的氢氧化反应相比,阴极发生的氧还原反应(ORR)是动力学缓慢的过程,严重阻碍了燃料电池的广泛应用,因此迫切需要开发高活性的电催化剂来降低其电化学过电位,提高反应动力学.铂基纳米晶是氧还原反应有效的电催化剂,但存在成本高、储量少且耐用性差等问题.将铂(Pt)与过渡金属(Fe,Co,Ni等)合金化可以提升催化活性,且最外层有序的Pt原子层可以有效地避免过渡金属的腐蚀溶解,同时,利用金(Au)与Pt基合金形成核壳结构可以有效地降低催化剂成本,同时增强稳定性.然而,在以Au作为核时,很难通过退火处理获得富含Pt层的核壳催化剂.本文利用钛(Ti)原子与Au原子合金化后的协同作用,成功地制备了核壳AuTi@PtNi氧还原催化剂.由于Ti与Au的强相互作用,使得该催化剂即使经高温退火处理,依旧可以使Au保持在内部,同时可以获得富Pt壳层.利用配备有电子能量损失谱的透射电子显微镜及X射线电子能谱对催化剂进行表征,结果表明,Ti的引入可大大提升催化剂的热稳定性.由于具有核壳结构及富Pt的PtNi壳层,退火后的AuTi@PtNi-400催化剂在0.9 V(RHE)时的质量比活性(5.26 A mgPt^(‒1))和面积比活性(2.72 mA cm^(‒2))分别是商业化Pt/C催化剂的19.26倍和9.84倍.另外,AuTi@PtNi-400催化剂在20000圈循环测试后质量活性衰减不到10%,稳定性好于商业化Pt/C催化剂和未经过退火的AuTi@PtNi催化剂.进一步对AuTi@PtNi-400进行电催化测试,结果表明,在功率密度达到0.61 W cm^(‒2)的同时可产生1.31 A cm^(‒2)的电流密度,该结果优于商业化Pt(1.05 A cm^(‒2)和0.34 W cm^(‒2))以及Ti-Au@PtNi/C(1.25 A cm^(‒2)和0.62 W cm^(‒2)),峰值功率密度高达0.80 W cm^(‒2),这表明所制备的Ti-Au@PtNi/C-400催化剂不仅在三电极体系中具有较好的性能,在电堆测试中也展现出高性能,可以较大地满足和促进燃料电池的发展和应用.综上所述,对于燃料电池阴极催化剂,可结合形貌工程及协调作用,制备出低成本高性能的ORR催化剂,为燃料电池的进一步应用提供新思路.展开更多
Achieving high activity and durability for the oxygen reduction reaction(ORR)with an ultra-low amount of platinum is significant to promote the widespread application of proton exchange membrane fuel cells(PEMFCs).Her...Achieving high activity and durability for the oxygen reduction reaction(ORR)with an ultra-low amount of platinum is significant to promote the widespread application of proton exchange membrane fuel cells(PEMFCs).Here we report a new ultrathin(∼1 nm)ternary PtNiGa alloy nanowires(PtNiGa NWs)electrocatalyst,in which the presence of gallium(Ga)enhances the oxidation resistance of platinum(Pt)and nickel(Ni)and suppresses the dissolution of Ni.The mass and specific activities of PtNiGa NWs are about 11.2 and 7.6 times higher than those of commercial Pt/C catalysts for ORR.Moreover,the mass activity of PtNiGa/C NWs nanocatalyst decreased only by 12.8%and largely retained its electrochemical surface area(ECSA)after 10,000 potential cycles,compared with 38%loss of ECSA for commercial Pt/C catalyst.Therefore,this work provides a general guideline for preparing ternary alloy electrocatalysts and enhancing the activity and stability of the cathode ORR reaction of PEMFCs.展开更多
文摘质子交换膜燃料电池(PEMFCs)将化学燃料转化为电能,具有能量转换效率高、清洁、零排放等特点,被认为是未来重要的能源利用装置.与阳极发生的氢氧化反应相比,阴极发生的氧还原反应(ORR)是动力学缓慢的过程,严重阻碍了燃料电池的广泛应用,因此迫切需要开发高活性的电催化剂来降低其电化学过电位,提高反应动力学.铂基纳米晶是氧还原反应有效的电催化剂,但存在成本高、储量少且耐用性差等问题.将铂(Pt)与过渡金属(Fe,Co,Ni等)合金化可以提升催化活性,且最外层有序的Pt原子层可以有效地避免过渡金属的腐蚀溶解,同时,利用金(Au)与Pt基合金形成核壳结构可以有效地降低催化剂成本,同时增强稳定性.然而,在以Au作为核时,很难通过退火处理获得富含Pt层的核壳催化剂.本文利用钛(Ti)原子与Au原子合金化后的协同作用,成功地制备了核壳AuTi@PtNi氧还原催化剂.由于Ti与Au的强相互作用,使得该催化剂即使经高温退火处理,依旧可以使Au保持在内部,同时可以获得富Pt壳层.利用配备有电子能量损失谱的透射电子显微镜及X射线电子能谱对催化剂进行表征,结果表明,Ti的引入可大大提升催化剂的热稳定性.由于具有核壳结构及富Pt的PtNi壳层,退火后的AuTi@PtNi-400催化剂在0.9 V(RHE)时的质量比活性(5.26 A mgPt^(‒1))和面积比活性(2.72 mA cm^(‒2))分别是商业化Pt/C催化剂的19.26倍和9.84倍.另外,AuTi@PtNi-400催化剂在20000圈循环测试后质量活性衰减不到10%,稳定性好于商业化Pt/C催化剂和未经过退火的AuTi@PtNi催化剂.进一步对AuTi@PtNi-400进行电催化测试,结果表明,在功率密度达到0.61 W cm^(‒2)的同时可产生1.31 A cm^(‒2)的电流密度,该结果优于商业化Pt(1.05 A cm^(‒2)和0.34 W cm^(‒2))以及Ti-Au@PtNi/C(1.25 A cm^(‒2)和0.62 W cm^(‒2)),峰值功率密度高达0.80 W cm^(‒2),这表明所制备的Ti-Au@PtNi/C-400催化剂不仅在三电极体系中具有较好的性能,在电堆测试中也展现出高性能,可以较大地满足和促进燃料电池的发展和应用.综上所述,对于燃料电池阴极催化剂,可结合形貌工程及协调作用,制备出低成本高性能的ORR催化剂,为燃料电池的进一步应用提供新思路.
基金supported by the National Youth Top-notch Talent Support Program of China,and the Sichuan Science and Technology Program(No.2020YJ0243)Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(No.2022-K28).
文摘Achieving high activity and durability for the oxygen reduction reaction(ORR)with an ultra-low amount of platinum is significant to promote the widespread application of proton exchange membrane fuel cells(PEMFCs).Here we report a new ultrathin(∼1 nm)ternary PtNiGa alloy nanowires(PtNiGa NWs)electrocatalyst,in which the presence of gallium(Ga)enhances the oxidation resistance of platinum(Pt)and nickel(Ni)and suppresses the dissolution of Ni.The mass and specific activities of PtNiGa NWs are about 11.2 and 7.6 times higher than those of commercial Pt/C catalysts for ORR.Moreover,the mass activity of PtNiGa/C NWs nanocatalyst decreased only by 12.8%and largely retained its electrochemical surface area(ECSA)after 10,000 potential cycles,compared with 38%loss of ECSA for commercial Pt/C catalyst.Therefore,this work provides a general guideline for preparing ternary alloy electrocatalysts and enhancing the activity and stability of the cathode ORR reaction of PEMFCs.
