Qi Ruikai, Jiang Qiuling, Deng Li, Yu Xianqiang, Shi Bingyan, Zhong Mengxiao, Wang Ying, Lu Xiaofeng
Alan G. MacDiarmid Institute, College of Chemistry, Jilin University Changchun 130012 P. R. China
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences Changchun 130022 China
Chem Sci. 2024 Nov 18;16(1):378-385. doi: 10.1039/d4sc06818a. eCollection 2024 Dec 18.
Constructing highly efficient electrocatalysts interface manipulation and structural design to facilitate rapid electron transfer in electrocatalytic nitrate-to-ammonia conversion is crucial to attaining superior NH yield rates. Here, a Mott-Schottky type electrocatalyst of Co/InO with a continuous fiber structure has been designed to boost the electrocatalytic nitrate-to-ammonia performance. The optimized Co/InO-1 catalyst exhibits an impressive NH yield rate of 70.1 mg cm h at -0.8 V the reversible hydrogen electrode (RHE), along with an NH faradaic efficiency (FE) of 93.34% at 0 V RHE, greatly outperforming the single-component Co and InO samples. The yield rate of Co/InO-1 is also superior to that of most currently reported Co-based catalysts and heterostructured ones. Evidence from experiments and theoretical results confirms the formation of a Mott-Schottky heterojunction, which achieves a Co site enriched with electrons, coupled with an InO facet enriched with holes, inducing an electron redistribution to promote the utilization of electroactive sites. Consequently, the reaction energy barrier for nitrate-to-ammonia conversion is significantly reduced, further enhancing its yield efficiency.
构建高效电催化剂——界面调控与结构设计以促进电催化硝酸盐制氨过程中的快速电子转移，对于实现优异的氨产率至关重要。在此，设计了一种具有连续纤维结构的莫特-肖特基型Co/In₂O₃电催化剂，以提升电催化硝酸盐制氨性能。优化后的Co/In₂O₃-1催化剂在相对于可逆氢电极（RHE）为-0.8 V时展现出令人印象深刻的70.1 mg cm⁻² h⁻¹的氨产率，以及在相对于RHE为0 V时93.34%的氨法拉第效率（FE），大大优于单组分Co和In₂O₃样品。Co/In₂O₃-1的产率也优于目前报道的大多数钴基催化剂和异质结构催化剂。实验和理论结果证据证实形成了莫特-肖特基异质结，其实现了富含电子的Co位点与富含空穴的In₂O₃晶面的耦合，诱导电子重新分布以促进电活性位点的利用。因此，硝酸盐制氨转化的反应能垒显著降低，进一步提高了其产率效率。
