Enhanced Activity Promoted by CeOx on a CoOx Electrocatalyst for the Oxygen Evolution Reaction

Kim, Junhyuk; Shin, Kihyun; Kawashima, Konosuke; Youn, Duck Hyun; Lin, Jie; Hong, Tae Eun; Liu, Yang; Wygant, Bryan R.; Wang, Joy; Henkelman, Graeme; Mullins, C. Buddie

doi:10.1021/acscatal.8b00820

Cited by 150 publications

(99 citation statements)

References 57 publications

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“…studies 42,67,68. For example, DFT calculations by Kim et al, demonstrated that CeO 2 can perturbe the electronic structure of Co species and further optimize the binding energy of intermediate oxygenated adsorbates 69. In view of the different work functions of Gd 2 O 3 and Co, the flow of electrons would occur through the metal/semiconductor interface;70 while Gd 2 O 3 as one of important REO may regulate the electronic structure of Co because the 4f orbital of Gd is available for electron sharing and bonding 71.…”

Section: Resultsmentioning

confidence: 99%

Gadolinium‐Induced Valence Structure Engineering for Enhanced Oxygen Electrocatalysis

Wang

Yang

et al. 2020

Advanced Energy Materials

124

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Rare earth doped materials with unique electronic ground state configurations are considered emerging alternatives to conventional Pt/C for the oxygen reduction reaction (ORR). Herein, gadolinium (Gd)‐induced valence structure engineering is, for the first, time investigated for enhanced oxygen electrocatalysis. The Gd2O3–Co heterostructure loaded on N‐doped graphene (Gd2O3–Co/NG) is constructed as the target catalyst via a facile sol–gel assisted strategy. This synthetic strategy allows Gd2O3–Co nanoparticles to distribute uniformly on an N‐graphene surface and form intimate Gd2O3/Co interface sites. Upon the introduction of Gd2O3, the ORR activity of Gd2O3–Co/NG is significantly increased compared with Co/NG, where the half‐wave potential (E1/2) of Gd2O3–Co/NG is 100 mV more positive than that of Co/NG and even close to commercial Pt/C. The density functional theory calculation and spectroscopic analysis demonstrate that, owing to intrinsic charge redistribution at the engineered interface of Gd2O3/Co, the coupled Gd2O3–Co can break the OOH*–OH* scaling relation and result in a good balance of OOH* and OH* binding on Gd2O3–Co surface. For practical application, a rechargeable Zn–air battery employing Gd2O3–Co/NG as an air–cathode achieves a large power density and excellent charge–discharge cycle stability.

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Section: Resultsmentioning

confidence: 99%

Gadolinium‐Induced Valence Structure Engineering for Enhanced Oxygen Electrocatalysis

Wang

Yang

et al. 2020

Advanced Energy Materials

124

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“…Unfortunately, the large‐scale utilization of these noble metals has been severely blocked by their limited abundance and high cost. As such, numerous endeavors have been undertaken to exploit for an alternative to noble catalysts during the past decades …”

Section: Introductionmentioning

confidence: 99%

Oriented Transformation of Co‐LDH into 2D/3D ZIF‐67 to Achieve Co–N–C Hybrids for Efficient Overall Water Splitting

Chen

Jia

et al. 2019

Advanced Energy Materials

277

141

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from electric energy into chemical energy, but also offers a promising platform for utilizing intermittently renewable energy sources (e.g., wind and solar). [1][2][3] To improve the splitting efficiency, precious Pt-based and Ir/Ru-based electrocatalysts are usually employed in the practical electro lysis to reduce the activation energy barriers of two core half-reactions involved in water splitting, i.e., hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. [4,5] Unfortunately, the large-scale utilization of these noble metals has been severely blocked by their limited abundance and high cost. As such, numerous endeavors have been undertaken to exploit for an alternative to noble catalysts during the past decades. [6][7][8][9][10] Emerging as a new class of crystalline materials, metal-organic frameworks (MOFs) constructed by bridging metal ions with organic linkers have drawn considerable attention to themselves owing to their porous, high specific surface, and tailorable features. [11][12][13][14] In recent years, MOFs have also been demonstrated as an ideal precursor to fabricate functional transition metal (TM)-carbon-based nanohybrids, which hold great promise as low-cost and efficient electrocatalysts for water splitting. [15][16][17][18][19][20] Since the chemical and the physical properties of the MOFsderived TM-carbon-based nanohybrids are highly dependent on the MOF precursors, it has been widely acknowledged that building MOF precursors with favorable composition, morphology, and surface structure is a prerequisite to enable these nanohybrids with satisfactory electrocatalytic activity. [21] To this end, there has been much attention surrounding the dedicate design of MOF precursors. [22][23][24][25][26][27][28][29][30][31][32] Currently, most work basically focus on the 3D MOF precursors owing to their high structural stability, large specific surface areas, and abundant pores. [24,25] After a refined post-treatment, their derived TM-carbon-based nanohybrids can inherit well original 3D nanostructure. Furthermore, the solid feature of MOF precursor is turned to the hollow counterpart sometimes. [26,27] These merits ensure the rapid mass transfer ability and rich potential active sites, thus improving the electrocatalytic activity. For instance, Pan et al. synthesized well-inherited hollow CoP@NC nanohybrids by direct calcination of well-performed core-shell CoZn-ZIF dodecahedra under Ar at 900 °C followed by an oxidationphosphorization process, which showed remarkable OER catalytic activity with an overpotential of 310 mV to drive a current Construction of well-defined metal-organic framework precursor is vital to derive highly efficient transition metal-carbon-based electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting. Herein, a novel strategy involving an in situ transformation of ultrathin cobalt layered double hydroxide into 2D cobalt zeolitic imidazolate framework (ZIF-67) nanosheets grafted with 3D ZIF-67 p...

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“…[32] The heterogeneous species is able to modulate MOF's nanostructure for improved surface area and accessible active sites. Most importantly, it is also anticipated to induce possible synergistic effect between different components via formation of defects, interfacial electronic coupling, and/or strain engineering, [3,[33][34][35][36][37] offering a great chance to optimize the adsorption energy of the critical intermediates, leading to improved intrinsic catalytic activity.…”

Section: Introductionmentioning

confidence: 99%

Strong Electronic Interaction Enhanced Electrocatalysis of Metal Sulfide Clusters Embedded Metal–Organic Framework Ultrathin Nanosheets toward Highly Efficient Overall Water Splitting

Zhao

et al. 2020

Advanced Science

135

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Unique metal sulfide (MS) clusters embedded ultrathin nanosheets of Fe/Ni metal-organic framework (MOF) are grown on nickel foam (NiFe-MS/MOF@NF) as a highly efficient bifunctional electrocatalyst for overall water splitting. It exhibits remarkable catalytic activity and stability toward both the oxygen evolution reaction (OER, ƞ = 230 mV at 50 mA cm −2) and hydrogen evolution reaction (HER, ƞ = 156 mV at 50 mA cm −2) in alkaline media, and bi-functionally catalyzes overall alkaline water splitting at a current density of 50 mA cm −2 by 1.74 V cell voltage without iR compensation. The enhancement mechanism is ascribed to the impregnated metal sulfide clusters in the nanosheets, which not only promote the formation of ultrathin nanosheet to greatly enlarge the reaction surface area while offering high electric conductivity, but more importantly, efficiently modulate the electronic structure of the catalytically active atom sites to an electron-rich state via strong electronic interaction and strengthen the adsorption of oxygenate intermediate to facilitate fast electrochemical reactions. This work reports a highly efficient HER/OER bifunctional electrocatalyst and may shed light on the rational design and synthesis of uniquely structured MOF-derived catalysts.

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Enhanced Activity Promoted by CeO_x on a CoO_x Electrocatalyst for the Oxygen Evolution Reaction

Cited by 150 publications

References 57 publications

Gadolinium‐Induced Valence Structure Engineering for Enhanced Oxygen Electrocatalysis

Gadolinium‐Induced Valence Structure Engineering for Enhanced Oxygen Electrocatalysis

Oriented Transformation of Co‐LDH into 2D/3D ZIF‐67 to Achieve Co–N–C Hybrids for Efficient Overall Water Splitting

Strong Electronic Interaction Enhanced Electrocatalysis of Metal Sulfide Clusters Embedded Metal–Organic Framework Ultrathin Nanosheets toward Highly Efficient Overall Water Splitting

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