High-valence metals improve oxygen evolution reaction performance by modulating 3d metal oxidation cycle energetics
High-valence metals improve oxygen evolution reaction performance by modulating 3d metal oxidation cycle energetics
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高价金属通过调节 3d 金属氧化循环能量来提高析氧反应性能
DOI：
10.1038/s41929-020-00525-6
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发表时间：
2020-10
期刊：
影响因子：
37.8
通讯作者：
Hu Yongf
中科院分区：
文献类型：
--
作者：
Zhang Bo;Wang Lie;Cao Zhen;Kozlov Sergey M.;Garcia de Arquer F Pelayo;Dinh Cao Thang;Li Jun;Wang Ziyun;Zheng Xueli;Zhang Longsheng;Wen Yunzhou;Voznyy Oleks;r;Comin Riccardo;De Luna Phil;Regier Tom;Bi Wenli;Alp E. Ercan;Pao Chih-Wen;Zheng Lirong;Hu Yongf
多金属氢氧化物在析氧反应中的催化性能优于贵金属催化剂。在这种基于3d金属的催化剂中，3d金属的氧化循环已经被假定为充当OER能量限制过程;然而，由于相邻3d金属调制器的电子结构之间的相似性，其能量学的进一步调整是具有挑战性的。在这里，我们报告了一种策略，重新编程的Fe，Co和Ni的氧化循环，通过将高价过渡金属调制器X（X = W，Mo，Nb，Ta，Re和MoW）。我们使用原位和非原位软X射线吸收光谱和硬X射线吸收光谱来表征调制NiFeX和FeCoX羟基氧化物催化剂的氧化转变，并得出结论，较低的OER过电位是由高价调制器使3d金属更容易的氧化转变所促进的。我们报告了~17倍的质量活性增强相比，广泛应用于工业水裂解电解槽的OER催化剂。多金属氢氧化物是碱性水氧化最活跃的催化剂之一，但调整其性能仍然是一个挑战。现在，NiFe基和FeCo基催化剂的性能通过掺入高价调制剂金属来优化，其将活性金属向低价态转移并实现较低的过电位。
Multimetal oxyhydroxides have recently been reported that outperform noble metal catalysts for oxygen evolution reaction (OER). In such 3d-metal-based catalysts, the oxidation cycle of 3d metals has been posited to act as the OER thermodynamic-limiting process; however, further tuning of its energetics is challenging due to similarities among the electronic structures of neighbouring 3d metal modulators. Here we report a strategy to reprogram the Fe, Co and Ni oxidation cycles by incorporating high-valence transition-metal modulators X (X = W, Mo, Nb, Ta, Re and MoW). We use in situ and ex situ soft and hard X-ray absorption spectroscopies to characterize the oxidation transition in modulated NiFeX and FeCoX oxyhydroxide catalysts, and conclude that the lower OER overpotential is facilitated by the readier oxidation transition of 3d metals enabled by high-valence modulators. We report an ~17-fold mass activity enhancement compared with that for the OER catalysts widely employed in industrial water-splitting electrolysers. Multimetal oxyhydroxides are among the most active catalysts for alkaline water oxidation, but tuning their properties remains a challenge. Now, the performance of NiFe- and FeCo-based catalysts is optimized with the incorporation of high-valence modulator metals, which shifts the active metals towards lower valence states and enables lower overpotentials.
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影响因子：
2.1
作者：
M. Novak;Z. Johan;R. Škoda;P. Černý;V. Šrein;F. Veselovský
通讯作者：
M. Novak;Z. Johan;R. Škoda;P. Černý;V. Šrein;F. Veselovský
影响因子：
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作者：
Roy, C.;Sebok, B.;Chorkendorff, I
通讯作者：
Chorkendorff, I
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Guan, Jingqi;Duan, Zhiyao;Li, Can
通讯作者：
Li, Can
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Friebel, Daniel;Louie, Mary W.;Bell, Alexis T.
通讯作者：
Bell, Alexis T.
影响因子：
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作者：
Seitz, Linsey C.;Dickens, Colin F.;Jaramillo, Thomas F.
通讯作者：
Jaramillo, Thomas F.