在镍位点具有电子定位的镍聚酞菁，用于增强 CO2 还原反应
Applied Catalysis B: Environment and Energy
(
IF
21.1
)
Pub Date : 2022-01-12
, DOI:
10.1016/j.apcatb.2022.121093
Kejun Chen
1
,
Maoqi Cao
1,
2
,
Ganghai Ni
1
,
Shanyong Chen
1
,
Hanxiao Liao
1
,
Li Zhu
1,
3
,
Hongmei Li
1
,
Junwei Fu
1
,
Junhua Hu
4
,
Emiliano Cortés
3
,
Min Liu
1
Affiliation
State Key Laboratory of Powder Metallurgy, School of Physical and Electronics, Central South University, Changsha 410083, China
School of Chemistry and Chemical Engineering, Qiannan Normal University for Nationalities, Duyun 558000, China
Nanoinstitut München, Fakultät für Physik, Ludwig-Maximilians-Universität München, 80539 München, Germany
School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450002, China
乍一看，镍酞菁 (NiPc) 是一种引人注目的 CO 2还原反应 (CO 2 RR) 催化剂，因为它具有 Ni-N 4位点。不幸的是，由于缺电子Ni位点的CO 2吸附和活化能力差，原始NiPc的催化活性较低。在此，我们开发了具有扩展共轭的镍聚酞菁 (NiPPc)，以调整 Ni 活性位点的电子密度。NiPPc 扩大的 π 共轭引起 d 电子局域化，增加 Ni 位点的电子密度，从而增强其 CO 2吸附和活化。因此，在流通池中负载在碳纳米管 (NiPPc/CNT) 上的 NiPPc对 CO 2 RR 具有 -300 mA cm -2的优异活性， CO 选择性为 99.8%，远高于分散在碳上的 NiPc纳米管。NiPPc/CNT在-100 mA cm -2的电流密度下对CO 2 RR 表现出超过30小时的出色稳定性，对CO的选择性超过99.7%。这项工作展示了一种调整催化位点电子密度的新方法。
"点击查看英文标题和摘要"
Nickel polyphthalocyanine with electronic localization at the nickel site for enhanced CO2 reduction reaction
Nickel phthalocyanine (NiPc) can be at first glance a compelling catalyst for CO2 reduction reaction (CO2RR) because of its Ni–N4 site. Unfortunately, the pristine NiPc possesses a low catalytic activity resulting from the poor CO2 adsorption and activation capabilities of the electron-deficiency Ni site. Herein, we develop nickel polyphthalocyanine (NiPPc) with extended conjugation to tailor the electronic density at the Ni active site. The enlarged π conjugation of NiPPc evokes the d-electrons localization, increasing the electronic density at the Ni site, which enhances its CO2 adsorption and activation. Consequently, NiPPc supported on carbon nanotubes (NiPPc/CNT) in a flow cell delivers an excellent activity of −300 mA cm−2 for CO2RR with the CO selectivity of 99.8%, which is much higher than that of NiPc dispersed on carbon nanotubes. NiPPc/CNT exhibits an outstanding stability for CO2RR of more than 30 h at a current density of −100 mA cm−2 with an ultrahigh selectivity for CO, exceeding 99.7%. This work showcases a new way of tuning the electronic density of catalytic sites.
更新日期：2022-01-18