Increased activity in the oxygen evolution reaction by Fe4+-induced hole states in perovskite La1−xSrxFeO3

2020 ◽  
Vol 8 (8) ◽  
pp. 4407-4415 ◽  
Author(s):  
Zechao Shen ◽  
Yongbin Zhuang ◽  
Weiwei Li ◽  
Xiaochun Huang ◽  
Freddy E. Oropeza ◽  
...  

Hole for faster OER: The hole state induced by Fe4+ promotes the OER process. It reduces the energy barrier for electron transfer at the interface and facilitates a faster electron transfer from reaction intermediates to the catalyst.

Author(s):  
Hanna Lyle ◽  
Suryansh Singh ◽  
Michael Paolino ◽  
Ilya Vinogradov ◽  
Tanja Cuk

The conversion of diffusive forms of energy (electrical and light) into short, compact chemical bonds by catalytic reactions regularly involves moving a carrier from an environment that favors delocalization to one that favors localization.


2020 ◽  
Vol 13 (12) ◽  
pp. 5143-5151 ◽  
Author(s):  
Zhi Liang Zhao ◽  
Qi Wang ◽  
Xiang Huang ◽  
Qi Feng ◽  
Shuang Gu ◽  
...  

A Ru vacancy decreases the energy barrier from O* to OOH*, thus dramatically enhancing the OER performance of defect-rich RuO2 nanosheets.


2021 ◽  
Author(s):  
Xiao Ren ◽  
Tianze Wu ◽  
Yuanmiao Sun ◽  
Yan Li ◽  
Guoyu Xian ◽  
...  

<p><a></a><a>The oxygen evolution reaction (OER) is the bottleneck that limits the energy efficiency of water-splitting. The process involves four electrons’ transfer and the generation of triplet state O<sub>2</sub> from singlet state species (OH<sup>- </sup>or H<sub>2</sub>O). Recently, explicit spin selection was described as a possible way to promote OER in alkaline conditions, but the specific spin-polarized kinetics remains unclear. </a><a></a><a>Here, we report that </a><a>by using ferromagnetic ordered catalysts as the spin polarizer for spin selection under </a><a></a><a>a constant magnetic field</a>, <a>the OER can be enhanced.</a> However, it does not applicable to non-ferromagnetic catalysts. We found that the spin <a>polarization occurs at the first electron transfer step in OER</a>, where <a></a><a>coherent spin exchange happens </a>between the <a></a><a>ferromagnetic</a> catalyst and the adsorbed oxygen species <a>with fast kinetics</a>, under the principle of spin angular momentum conservation. In the next three electron transfer steps, as the adsorbed O species adopt fixed spin direction, the OER electrons need to follow the Hund rule and Pauling exclusion principle, thus to carry out spin polarization spontaneously and finally lead to the generation of triplet state O<sub>2</sub>. Here, we showcase spin-polarized kinetics of oxygen evolution reaction, which gives references in the understanding and design of spin-dependent catalysts.</p>


Author(s):  
Areeba Hameed ◽  
Khulood Logade ◽  
Naba Ali ◽  
Priya Ghosh ◽  
Sadiya Shafath ◽  
...  

Lanthanum based electrocatalytically active perovskites, LaMO3 (M=Cr, Mn, Fe, Co, Ni), were synthesized using a single step solution combustion synthesis technique. The perovskites showed exceptional performance for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline medium. Based on the experimental results and literature survey, it is suggested that the exceptional activity of Mn and Co based lanthanum perovskite catalyst could be due to the optimum stabilization of reaction intermediates involved in the rate-determining step (RDS) of ORR/OER. According to crystal field theory (CFT), the d-orbital of transition metals are affected by the octahedral arrangement of six negative charges around it. The d orbital degenerates by splitting into two high energy (eg) and three lower energy orbitals (t2g) while maintaining the same average energy level. The rate-determining step in the ORR/OER reaction that based on the eg orbital filling of B site transition metal cations If the d-electrons are less, the valence state goes up and lowering the eg orbital filling that results in strong adsorption of oxygenated species on the B site (strong B-OH bond). This strong bonding limits the overall reaction rate by the slow desorption of OH and its derivatives during ORR/OER. Similarly, too high eg filling causes weak adsorption of oxygenated species that limits the reaction through the slow adsorption of reactants. Therefore, to enhance the activity of ORR/OER reaction it is required to balance the adsorption and desorption of the reactants and the intermediate respectively. The better way is to optimize the eg orbital filling to be nearly 1 (eg = 1).Based on the experimental results and literature survey, it is suggested that the exceptional activity of Mn and Co based lanthanum perovskite catalyst could be due to the optimum stabilization of reaction intermediates involved in the rate-determining step (RDS) of ORR and OER.


2019 ◽  
Vol 7 (38) ◽  
pp. 22063-22069 ◽  
Author(s):  
Tong Wu ◽  
Shaoning Zhang ◽  
Kejun Bu ◽  
Wei Zhao ◽  
Qingyuan Bi ◽  
...  

The extraordinary oxygen evolution reaction (OER) in alkaline fuel cells and water-splitting systems demands a high electron transfer rate and catalysts with numerous active sites and massive hydroxyl groups.


2014 ◽  
Vol 16 (27) ◽  
pp. 13682-13688 ◽  
Author(s):  
Niels Bendtsen Halck ◽  
Valery Petrykin ◽  
Petr Krtil ◽  
Jan Rossmeisl

Oxygen evolution catalysis is restricted by the interdependence of adsorption energies of the reaction intermediates and the surface reactivity.


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Xiao Ren ◽  
Tianze Wu ◽  
Yuanmiao Sun ◽  
Yan Li ◽  
Guoyu Xian ◽  
...  

AbstractThe oxygen evolution reaction (OER) is the bottleneck that limits the energy efficiency of water-splitting. The process involves four electrons’ transfer and the generation of triplet state O2 from singlet state species (OH- or H2O). Recently, explicit spin selection was described as a possible way to promote OER in alkaline conditions, but the specific spin-polarized kinetics remains unclear. Here, we report that by using ferromagnetic ordered catalysts as the spin polarizer for spin selection under a constant magnetic field, the OER can be enhanced. However, it does not applicable to non-ferromagnetic catalysts. We found that the spin polarization occurs at the first electron transfer step in OER, where coherent spin exchange happens between the ferromagnetic catalyst and the adsorbed oxygen species with fast kinetics, under the principle of spin angular momentum conservation. In the next three electron transfer steps, as the adsorbed O species adopt fixed spin direction, the OER electrons need to follow the Hund rule and Pauling exclusion principle, thus to carry out spin polarization spontaneously and finally lead to the generation of triplet state O2. Here, we showcase spin-polarized kinetics of oxygen evolution reaction, which gives references in the understanding and design of spin-dependent catalysts.


2021 ◽  
Author(s):  
Xiwen Du ◽  
Zhe Li ◽  
Yi Feng ◽  
Xiuyao Lang ◽  
Wenjing Kang ◽  
...  

In this study, a core-shell structure (Ag@Co3O4) was constructed to modify valance state of cobalt cations precisely by continuously adjusting the shell thickness. There exists a volcano relationship between valence...


2020 ◽  
Vol 8 (6) ◽  
pp. 3311-3321 ◽  
Author(s):  
Zhengxin Qian ◽  
Keke Wang ◽  
Kexin Shi ◽  
Zhaoqin Fu ◽  
Zequn Mai ◽  
...  

A facile strategy is developed to create a MIL-88A/Ni(OH)2 heterostructure, where the interfacial charge transfer significantly boosted the OER performance.


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