In this work, two different functionalized graphene oxide (GO), sulfonic acid functionalized GO (SGO) and amino functionalized GO (NGO), were synthesized and incorporated into the sulfonated poly(arylene ether nitrile) (SPEN) by single doping and codoping. It was found that the codoping of SGO and NGO contributed to the enhancement of proton exchange membrane performance. These two functionalized GO as fillers were uniformly dispersed in SPEN matrix and their synergistic effect created the long-range proton transfer channels along fillers/SPEN matrix interfaces. Meanwhile, acid-base pairs which was induced by strong interfacial interactions between fillers and SPEN matrix provided new and low-energy-barrier pathways for proton hopping, facilitating the proton conduction via Grotthuss mechanism. Among all the membranes, the codoped S/N-3 composite membrane exhibited the highest proton conductivity (0.064 S·cm⁻¹ at 20 °C and 0.21 S·cm⁻¹ at 80 °C). Besides, it was endowed with unprecedented dimensional stability, especially in high temperature (just 12.75% at 80 °C). Also, low methanol permeability was conferred owing to methanol trapping effect of two functionalized GO. Furthermore, S/N-3 composite membrane showed a superior selectivity of 4.48 × 10⁵S⋅cm⁻³⋅s, which was nearly 10 times of that of commercialized Nafion 117. Our investigation provides a new strategy on the design of high performance composite membranes for applications of PEMs and other related fields.

在这项工作中，合成了两种不同的官能化氧化石墨烯（GO），磺酸官能化的GO（SGO）和氨基官能化的GO（NGO），并通过一次掺杂和共掺杂将其掺入磺化的聚亚芳基醚腈（SPEN）中。发现SGO和NGO的共掺杂有助于提高质子交换膜的性能。这两种作为填充剂的功能化GO均匀地分散在SPEN基质中，它们的协同作用沿着填充剂/ SPEN基质界面形成了长距离质子传递通道。同时，由填料与SPEN基质之间的强界面相互作用引起的酸碱对为质子跳跃提供了新的和低能垒的途径，从而促进了Grotthuss机理的质子传导。在所有的膜中^-1在20°C和0.21 S·cm ^-1在80°C）。此外，它还具有前所未有的尺寸稳定性，尤其是在高温下（80°C时仅为12.75％）。另外，由于两个官能化的GO的甲醇捕集作用，赋予了低的甲醇渗透性。此外，S / N-3的复合膜显示出4.48×10优良的选择性⁵ S⋅cm ^-3 ⋅s，这是那商品化的Nafion 117我们的调查的近10倍提供的高性能设计的新策略用于PEM和其他相关领域的复合膜。