通过调节氧还原反应途径利用二磷化铂纳米晶体实现可扩展的中性HO电合成。

Scalable neutral HO electrosynthesis by platinum diphosphide nanocrystals by regulating oxygen reduction reaction pathways.

作者信息

Li Hui, Wen Peng, Itanze Dominique S, Hood Zachary D, Adhikari Shiba, Lu Chang, Ma Xiao, Dun Chaochao, Jiang Lin, Carroll David L, Qiu Yejun, Geyer Scott M

机构信息

Department of Chemistry, Wake Forest University, Winston-Salem, NC, 27106, USA.

Shenzhen Engineering Lab of Flexible Transparent Conductive Films, School of Materials Science and Engineering, Harbin Institute of Technology, Shenzhen, 518055, China.

出版信息

Nat Commun. 2020 Aug 6;11(1):3928. doi: 10.1038/s41467-020-17584-9.

Despite progress in small scale electrocatalytic production of hydrogen peroxide (HO) using a rotating ring-disk electrode, further work is needed to develop a non-toxic, selective, and stable O-to-HO electrocatalyst for realizing continuous on-site production of neutral hydrogen peroxide. We report ultrasmall and monodisperse colloidal PtP nanocrystals that achieve HO production at near zero-overpotential with near unity HO selectivity at 0.27 V vs. RHE. Density functional theory calculations indicate that P promotes hydrogenation of OOH* to HO by weakening the Pt-OOH* bond and suppressing the dissociative OOH* to O* pathway. Atomic layer deposition of AlO prevents NC aggregation and enables application in a polymer electrolyte membrane fuel cell (PEMFC) with a maximum r(HO) of 2.26 mmol h cm and a current efficiency of 78.8% even at a high current density of 150 mA cm. Catalyst stability enables an accumulated neutral HO concentration in 600 mL of 3.0 wt% (pH = 6.6).

尽管在使用旋转环盘电极小规模电催化生产过氧化氢（HO）方面取得了进展，但仍需要进一步开展工作，以开发一种无毒、选择性好且稳定的从O到HO的电催化剂，以实现中性过氧化氢的连续现场生产。我们报道了超小且单分散的胶体PtP纳米晶体，其在相对于可逆氢电极（RHE）为0.27 V时，能在接近零过电位下实现HO的生产，且HO选择性接近100%。密度泛函理论计算表明，P通过削弱Pt - OOH键并抑制OOH解离为O的途径，促进了OOH加氢生成HO。AlO的原子层沉积可防止纳米晶体聚集，并使其能够应用于聚合物电解质膜燃料电池（PEMFC）中，即使在150 mA cm的高电流密度下，其最大r(HO)为2.26 mmol h cm，电流效率为78.8%。催化剂的稳定性使得在600 mL 3.0 wt%（pH = 6.6）的溶液中能够积累中性HO。