scholarly journals Single Co3O4 Nanocubes Electrocatalyzing the Oxygen Evolution Reaction: Nano-Impact Insights into Intrinsic Activity and Support Effects

2021 ◽  
Vol 22 (23) ◽  
pp. 13137
Author(s):  
Zhibin Liu ◽  
Manuel Corva ◽  
Hatem M. A. Amin ◽  
Niclas Blanc ◽  
Julia Linnemann ◽  
...  

Single-entity electrochemistry allows for assessing electrocatalytic activities of individual material entities such as nanoparticles (NPs). Thus, it becomes possible to consider intrinsic electrochemical properties of nanocatalysts when researching how activity relates to physical and structural material properties. Conversely, conventional electrochemical techniques provide a normalized sum current referring to a huge ensemble of NPs constituting, along with additives (e.g., binders), a complete catalyst-coated electrode. Accordingly, recording electrocatalytic responses of single NPs avoids interferences of ensemble effects and reduces the complexity of electrocatalytic processes, thus enabling detailed description and modelling. Herein, we present insights into the oxygen evolution catalysis at individual cubic Co3O4 NPs impacting microelectrodes of different support materials. Simulating diffusion at supported nanocubes, measured step current signals can be analyzed, providing edge lengths, corresponding size distributions, and interference-free turnover frequencies. The provided nano-impact investigation of (electro-)catalyst-support effects contradicts assumptions on a low number of highly active sites.

Author(s):  
Kaiyao Wu ◽  
Fei Chu ◽  
Yuying Meng ◽  
Kaveh Edalati ◽  
Qingsheng Gao ◽  
...  

Transition metal-based amorphous alloys have attracted increasing attention as precious-metal-free electrocatalysts for oxygen evolution reaction (OER) of water splitting due to their high macro-conductivity and abundant surface active sites. However,...


2021 ◽  
Author(s):  
Qiaoling Kang ◽  
Dawei Lai ◽  
Wenyin Tang ◽  
Qingyi Lu ◽  
Feng Gao

Effective strategies to increase the intrinsic activity by electronic modulation and to increase the number of active sites by structural design are discussed for improving the oxygen evolution activities of NiFe alloys.


2019 ◽  
Vol 11 (1) ◽  
Author(s):  
Kaili Zhang ◽  
Xinhui Xia ◽  
Shengjue Deng ◽  
Yu Zhong ◽  
Dong Xie ◽  
...  

Abstract Controllable synthesis of highly active micro/nanostructured metal electrocatalysts for oxygen evolution reaction (OER) is a particularly significant and challenging target. Herein, we report a 3D porous sponge-like Ni material, prepared by a facile hydrothermal method and consisting of cross-linked micro/nanofibers, as an integrated binder-free OER electrocatalyst. To further enhance the electrocatalytic performance, an N-doping strategy is applied to obtain N-doped sponge Ni (N-SN) for the first time, via NH3 annealing. Due to the combination of the unique conductive sponge structure and N doping, the as-obtained N-SN material shows improved conductivity and a higher number of active sites, resulting in enhanced OER performance and excellent stability. Remarkably, N-SN exhibits a low overpotential of 365 mV at 100 mA cm−2 and an extremely small Tafel slope of 33 mV dec−1, as well as superior long-term stability, outperforming unmodified sponge Ni. Importantly, the combination of X-ray photoelectron spectroscopy and near-edge X-ray adsorption fine structure analyses shows that γ-NiOOH is the surface-active phase for OER. Therefore, the combination of conductive sponge structure and N-doping modification opens a new avenue for fabricating new types of high-performance electrodes with application in electrochemical energy conversion devices.


2019 ◽  
Author(s):  
Lichen Bai ◽  
Chia-Shuo Hsu ◽  
Duncan Alexander ◽  
Hao Ming Chen ◽  
Xile Hu

Single atom catalysts exhibit well-defined active sites and potentially maximum atomic efficiency. However, they are unsuitable for reactions that benefit from bimetallic promotion such as the oxygen evolution reaction (OER) in alkaline medium. Here we show that a single atom Co precatalyst can be in-situ transformed into a Co-Fe double atom catalyst for OER. This catalyst exhibits one of the highest turnover frequencies among metal oxides. Electrochemical, microscopic, and spectroscopic data including those from operando X-ray absorption spectroscopy, reveal a dimeric Co-Fe moiety as the active site of the catalyst. This work demonstrates double-atom catalysis as a promising approach for the developed of defined and highly active OER catalysts.


2020 ◽  
Author(s):  
Likun Gao ◽  
Xun Cui ◽  
Zewei Wang ◽  
Christopher Sewell ◽  
Zili Li ◽  
...  

Abstract The ability to develop highly active and low-cost electrocatalysts represents an important endeavor toward accelerating sluggish water-oxidation kinetics. Herein, we report, for the first time, the implementation and unravelling of photothermal effect of spinel nanoparticles (NPs) on promoting dynamic active sites generation to markedly enhance their oxygen evolution reaction (OER) activity via an integrated operando Raman and density functional theory (DFT) study. Specifically, NiFe2O4 (NFO) NPs are first synthesized by capitalizing on amphiphilic star-like diblock copolymers as nanoreactors. Upon the NIR light irradiation, the photothermal heating of the NFO-based electrode progressively raises the temperature, accompanied by a marked decrease of overpotential. Accordingly, only an overpotential of 309 mV is required to yield a high current density of 100 mA cm-2, greatly lower than recently-reported earth-abundant electrocatalysts. More importantly, photothermal effect of NFO NPs not only significantly reduces the activation energy necessitated for water splitting, but also facilitates surface reconstruction into high-active oxyhydroxides at lower potential (1.36 V) under OER conditions, as revealed by operando Raman spectra-electrochemistry. Moreover, the DFT calculation corroborates that these reconstructed (Ni,Fe)oxyhydroxides are electrocatalytically active sites as the kinetics barrier is largely reduced over pure NFO without surface reconstruction. Given the diversity of materials (metal oxides, sulfides, phosphides, etc.) possessing the photo-to-thermal conversion, this effect may thus provide a unique and robust platform to boost highly-active surface species in nanomaterials for fundamental understanding of enhanced performance that may underpin future advances in electrocatalysis, photocatalysis, solar energy conversion and renewable energy production.  


2021 ◽  
Author(s):  
Chengan Liao ◽  
Ziyi Xiao ◽  
Ning Zhang ◽  
Bo Liang ◽  
Gen Chen ◽  
...  

A facile photo-irradiation method is developed to tune active sites over β-Ni(OH)2 nanosheets. Photo-irradiated β-Ni(OH)2 nanosheets possess disordered surface atoms and preferred growth of highly active crystal face, which exhibits...


2016 ◽  
Vol 138 (38) ◽  
pp. 12552-12563 ◽  
Author(s):  
Hyung-Suk Oh ◽  
Hong Nhan Nong ◽  
Tobias Reier ◽  
Arno Bergmann ◽  
Manuel Gliech ◽  
...  

2019 ◽  
Author(s):  
Lichen Bai ◽  
Chia-Shuo Hsu ◽  
Duncan Alexander ◽  
Hao Ming Chen ◽  
Xile Hu

Single atom catalysts exhibit well-defined active sites and potentially maximum atomic efficiency. However, they are unsuitable for reactions that benefit from bimetallic promotion such as the oxygen evolution reaction (OER) in alkaline medium. Here we show that a single atom Co precatalyst can be in-situ transformed into a Co-Fe double atom catalyst for OER. This catalyst exhibits one of the highest turnover frequencies among metal oxides. Electrochemical, microscopic, and spectroscopic data including those from operando X-ray absorption spectroscopy, reveal a dimeric Co-Fe moiety as the active site of the catalyst. This work demonstrates double-atom catalysis as a promising approach for the developed of defined and highly active OER catalysts.


2019 ◽  
Vol 7 (18) ◽  
pp. 10949-10953 ◽  
Author(s):  
Wei Wang ◽  
Yajun Zhang ◽  
Xiaojuan Huang ◽  
Yingpu Bi

FeVO4 nanobelts bounded by {010} facets exhibit much higher OER activities and lower overpotential than nanosheets enclosed by {010} facets, which were mainly attributed to the favorable atomic arrangements of {010} facets with Fe–V dual-active sites and an open surface structure.


2019 ◽  
Vol 55 (53) ◽  
pp. 7687-7690 ◽  
Author(s):  
Can Huang ◽  
Ying Zou ◽  
Ya-Qian Ye ◽  
Ting Ouyang ◽  
Kang Xiao ◽  
...  

The highly active and stable oxygen evolution reaction (OER) performance of Ni–Fe phosphide/metaphosphate (Ni1−xFex-P/PO3) can originate from in situ generated Fe doped γ-NiOOH.


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