Zichang Zhang, Tongyu Liu, Xi Zhang, Chenjun Zhang, Xu Jin, Jie Zheng, Qiang Sun
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引用次数: 0
Abstract
Dodecahydro-N-ethylcarbazole (12H-NEC) is regarded as the most promising liquid organic hydrogen carrier for hydrogen storage and transportation. Understanding the mechanism of 12H-NEC dehydrogenation and developing cost-effective catalysts are significant. Pd is a high-performance catalyst for 12H-NEC but is not cost-effective, and Ni is just the opposite. How to understand the whole process of full dehydrogenation and improve the performance of Ni become two key questions. Herein, we systematically investigated the mechanism of the full dehydrogenation of 12H-NEC on Pd(111) and Ni(111) for the first time. By calculating all the barriers in the whole dehydrogenation process, we identified that 3H-NEC to 2H-NEC is the rate-determining step and Ni is catalytically less effective than Pd, which is attributed to its narrower d-band distribution and a 0.32 eV higher d-band center than that of Pd. To improve the performance of Ni, we further introduced dopants of Au, Ag, Cu, Pd, Pt, Ru, Rh, Zn, and Al. We found that Ag doping brings a downshift of the d-band center from -1.29 to -1.67 eV and reduces the barrier of 4H-NEC to NEC from 0.94 to 0.76 eV. This study provides new insights into the catalytic mechanism and performance-tuning strategy to help future experimental synthesis.
十二氢-N-乙基咔唑(12H-NEC)被认为是最有希望用于氢储存和运输的液态有机氢载体。了解 12H-NEC 的脱氢机理和开发具有成本效益的催化剂意义重大。Pd 是 12H-NEC 的高性能催化剂,但成本效益不高,而 Ni 则恰恰相反。如何理解全脱氢的全过程和提高 Ni 的性能成为两个关键问题。在此,我们首次系统地研究了 12H-NEC 在 Pd(111) 和 Ni(111) 上完全脱氢的机理。通过计算整个脱氢过程中的所有势垒,我们发现 3H-NEC 到 2H-NEC 是决定速率的一步,而镍的催化效率低于钯,这是因为镍的 d 带分布较窄,d 带中心比钯高 0.32 eV。为了提高 Ni 的性能,我们进一步引入了 Au、Ag、Cu、Pd、Pt、Ru、Rh、Zn 和 Al 等掺杂剂。我们发现,掺杂 Ag 使 d 带中心从-1.29 eV 下移到-1.67 eV,并将 4H-NEC 到 NEC 的势垒从 0.94 eV 降低到 0.76 eV。这项研究为催化机理和性能调整策略提供了新的见解,有助于未来的实验合成。
期刊介绍:
ACS Applied Materials & Interfaces is a leading interdisciplinary journal that brings together chemists, engineers, physicists, and biologists to explore the development and utilization of newly-discovered materials and interfacial processes for specific applications. Our journal has experienced remarkable growth since its establishment in 2009, both in terms of the number of articles published and the impact of the research showcased. We are proud to foster a truly global community, with the majority of published articles originating from outside the United States, reflecting the rapid growth of applied research worldwide.