National Institute of Advanced Industrial Science and Technology (AIST) , Ikeda, Osaka 563-8577, Japan.
Toyama National College of Technology , 13, Hongo-machi, Toyama, 939-8630, Japan.
J Am Chem Soc. 2015 Sep 16;137(36):11743-8. doi: 10.1021/jacs.5b06707. Epub 2015 Sep 8.
Ultrafine palladium nanoparticles (Pd NPs) supported on carbon nanospheres have been successfully synthesized using a facile methanol-mediated weakly-capping growth approach (WCGA) with anhydrous methanol as a mild reductant and a weakly capping agent. The Pd NPs show exceedingly high catalytic activity for 100% selective dehydrogenation of aqueous formic acid (FA) at ambient temperatures. The small size and clean surface of the Pd NPs greatly improve the catalytic properties of the as-prepared catalyst, providing an average rate of CO-free H2 generation up to 43 L H2 gPd(-1) min(-1) and a turnover frequency of 7256 h(-1) at 60 °C. These values are much higher than those obtained even with the most active catalyst reported thus far for heterogeneously catalyzed dehydrogenation of FA. This remarkably facile and effective methanol-mediated WCGA provides a powerful entry into ultrafine metal NPs with clean surface to achieve enhanced performance. Moreover, the catalytic results open up new avenues in the effective applications of FA for hydrogen storage.
在无水甲醇作为温和还原剂和弱配体的条件下，成功地利用简便的甲醇介导的弱配位生长方法（WCGA）合成了负载在碳球上的超细钯纳米粒子（Pd NPs）。Pd NPs 在环境温度下对甲酸（FA）的 100%选择性脱氢反应表现出极高的催化活性。Pd NPs 的小尺寸和清洁表面极大地提高了所制备催化剂的催化性能，提供了高达 43 L H2 gPd(-1) min(-1)的 CO 免费 H2 生成平均速率和 7256 h(-1)的转化率频率在 60°C 时。这些值远高于迄今为止报道的用于 FA 均相催化脱氢的最活跃催化剂所获得的值。这种简便有效的甲醇介导的 WCGA 为获得清洁表面的超细金属 NPs 提供了一种增强性能的有力途径。此外，催化结果为 FA 在储氢方面的有效应用开辟了新途径。
