Andaveh Reza, Sabour Rouhaghdam Alireza, Seif Abdolvahab, Wang Kun, Maleki Meysam, Ai Jianping, Barati Darband Ghasem, Li Jinyang
Department of Materials Engineering, Faculty of Engineering, Tarbiat Modares University, Tehran 14115111, P.O. Box: 14115-143, Iran.
Dipartimento di Fisica e Astronomia "G. Galilei", Università di Padova, via Marzolo 8, Padova I-35131, Italy.
ACS Appl Mater Interfaces. 2024 Feb 21;16(7):8717-8732. doi: 10.1021/acsami.3c16122. Epub 2024 Feb 7.
Urea electrolysis is a promising energy-efficient hydrogen production process with environmental benefits, but the lack of efficient and sustainable ampere-level current density electrocatalysts fabricated through simple methods is a major challenge for commercialization. Herein, we present an efficient and stable heterostructure electrocatalyst for full urea and water electrolysis in a convenient and time-efficient preparation manner. Overall, superhydrophilic/superaerophobic CoMn/CuNiP/NF exhibits exceptional performance for the hydrogen evolution reaction (HER) (-33.8, -184.4, and -234.8 mV at -10, -500, and -1000 mA cm, respectively), urea electro-oxidation reaction (UOR) [1.28, 1.43, and 1.51 V (vs RHE) at 10, 500, and 1000 mA cm, respectively], and oxygen evolution reaction (OER) [1.45, 1.67, and 1.74 V (vs RHE) at 10, 500, and 1000 mA cm, respectively]. Moreover, the superaerophobic CoMn/CuNiP/NF demonstrates promising potential in full urea (1.33, 1.57, and 1.60 V at 10, 500, and 1000 mA cm, respectively) and water (1.46 V, 1.78, and 1.86 at 10, 500, and 1000 mA cm, respectively) electrolysis. Based on X-ray photoelectron spectroscopy results, it was determined that the surface of the CoMn/CuNiP electrode was rich in redox pairs such as Ni/Ni, Cu/Cu, Co/Co, and Mn/Mn, which are crucial for the formation of active sites for the OER and UOR, such as NiOOH, MnOOH, and CoOOH, thereby enhancing the catalytic activity. Besides, the in situ assembled CoMn/CuNiP/NF displayed highly stable performance for HER, OER, and UOR with high Faradaic efficiency for over 500 h. This research offers a simple and efficient method for manufacturing a high-efficiency and stable trifunctional electrocatalyst capable of delivering ampere-level current density in urea-assisted hydrogen production. Our density functional theory calculations reveal the potential of CoMn/CuNiP as an effective catalyst, enhancing the electronic properties and catalytic performance. The near-zero Gibbs free-energy change for HER underscores its promise, while reduced CO desorption energies and charge redistribution support efficient UOR. These findings signify CoMn/CuNiP's potential for electrochemical applications.
尿素电解是一种具有环境效益且前景广阔的高效制氢工艺，但缺乏通过简单方法制备的高效且可持续的安培级电流密度电催化剂是商业化的一大挑战。在此，我们以简便且省时的制备方式展示了一种用于全尿素和水电解的高效稳定异质结构电催化剂。总体而言，超亲水/超疏气的CoMn/CuNiP/NF在析氢反应（HER）中表现出卓越性能（在-10、-500和-1000 mA cm时分别为-33.8、-184.4和-234.8 mV）、尿素电氧化反应（UOR）[在10、500和1000 mA cm时分别为1.28、1.43和1.51 V（相对于可逆氢电极，RHE）]以及析氧反应（OER）[在10、500和1000 mA cm时分别为1.45、1.67和1.74 V（相对于RHE）]。此外，超疏气的CoMn/CuNiP/NF在全尿素电解（在10、500和1000 mA cm时分别为1.33、1.57和1.60 V）和水电解（在10、500和1000 mA cm时分别为1.46 V、1.78和1.86）中展现出良好潜力。基于X射线光电子能谱结果，确定CoMn/CuNiP电极表面富含诸如Ni/Ni、Cu/Cu、Co/Co和Mn/Mn等氧化还原对，这些对于形成OER和UOR的活性位点（如NiOOH、MnOOH和CoOOH）至关重要，从而增强了催化活性。此外，原位组装的CoMn/CuNiP/NF在HER、OER和UOR中表现出高度稳定的性能，法拉第效率高，且可持续超过500小时。本研究提供了一种简单有效的方法来制造一种高效稳定的三功能电催化剂，该催化剂能够在尿素辅助制氢中提供安培级电流密度。我们的密度泛函理论计算揭示了CoMn/CuNiP作为有效催化剂的潜力，增强了电子性质和催化性能。HER近乎零的吉布斯自由能变化突出了其前景，而降低的CO脱附能和电荷重新分布支持了高效的UOR。这些发现表明CoMn/CuNiP在电化学应用中的潜力。
