The mechanism of water oxidation using transition metal-based heterogeneous electrocatalysts

Chemical Society Reviews, Год журнала: 2024, Номер 53(11), С. 5593 - 5625

Опубликована: Янв. 1, 2024

The oxygen evolution reaction (OER) mechanisms using transition metal-based electrocatalysts are instrumental in providing novel insights into both natural and artificial energy conversion processes.

Язык: Английский

---

Tuning synergy between nickel and iron in Ruddlesden–Popper perovskites through controllable crystal dimensionalities towards enhanced oxygen‐evolving activity and stability

Carbon Energy, Год журнала: 2024, Номер 6(6)

Опубликована: Фев. 8, 2024

Abstract Ni–Fe‐based oxides are among the most promising catalysts developed to date for bottleneck oxygen evolution reaction (OER) in water electrolysis. However, understanding and mastering synergy of Ni Fe remain challenging. Herein, we report that between can be tailored by crystal dimensionality Ni, Fe‐contained Ruddlesden–Popper (RP)‐type perovskites (La 0.125 Sr 0.875 ) n +1 (Ni 0.25 0.75 O 3 ( = 1, 2, 3), where material with shows best OER performance alkaline media. Soft X‐ray absorption spectroscopy spectra before after reveal enhanced Ni/Fe–O covalency boost electron transfer as compared those 1 2. Further experimental investigations demonstrate ion is active site stable this system, such unique reaches optimum at 3. Besides, increases, proportion unstable rock‐salt layers accordingly decreases leaching ions (especially 2+ into electrolyte suppressed, which induces a decrease ions, ultimately leading stability. This work provides new avenue rational catalyst design through dimensional strategy.

Язык: Английский

---

Metal‐Organic Frameworks: Direct Synthesis by Organic Acid‐Etching and Reconstruction Disclosure as Oxygen Evolution Electrocatalysts

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(11)

Опубликована: Янв. 22, 2024

Abstract Metal‐organic frameworks (MOFs) have emerged as promising oxygen evolution reaction (OER) electrocatalysts. Chemically bonded MOFs on supports are desirable yet lacking in routine synthesis, they may allow variable structural and the underlying structure‐activity relationship to be disclosed. Herein, direct MOF synthesis is achieved by an organic acid‐etching strategy (AES). Using π‐conjugated ferrocene (Fc) dicarboxylic acid etching agent ligand, a series of MFc‐MOF (M=Ni, Co, Fe, Zn) nanosheets synthesized metal supports. The crystal structure studied using X‐ray diffraction low‐dose transmission electron microscopy, which quasi ‐lattice‐matched with that metal, enabling situ growth. Operando Raman attenuated total reflectance Fourier transform infrared spectroscopy disclose NiFc‐MOF features dynamic rebuilding during OER. reconstructed one showing optimized electronic structures upshifted d ‐band center, high M−O bonding state occupancy, localized electrons adsorbates indicated density functional theory calculations, exhibits outstanding OER performance fairly low overpotential (130 mV at 10 mA cm −2 ) good stability (144 h). newly established approach for reconstruction disclosure stimulate development more prudent catalysts advancing

Язык: Английский

---

Coordination Tuning of Metal Porphyrins for Improved Oxygen Evolution Reaction

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(38)

Опубликована: Авг. 8, 2023

Abstract The nucleophilic attack of water or hydroxide on metal‐oxo units forms an O−O bond in the oxygen evolution reaction (OER). Coordination tuning to improve this is intriguing but has been rarely realized. We herein report improved OER catalysis by metal porphyrin 1‐M (M=Co, Fe) with a coordinatively unsaturated ion. designed and synthesized sterically blocking one side tethered tetraazacyclododecane unit. With protection, species generated can maintain unoccupied trans axial site. Importantly, displays higher activity alkaline solutions than analogues lacking such protection decreasing up 150‐mV overpotential achieve 10 mA/cm 2 current density. Theoretical studies suggest that site, unit becomes more positively charged thus favoured for as compared bearing ligands.

Язык: Английский

---

Non‐Noble‐Metal‐Based Electrocatalysts for Acidic Oxygen Evolution Reaction: Recent Progress, Challenges, and Perspectives

Small, Год журнала: 2024, Номер 20(48)

Опубликована: Авг. 25, 2024

Abstract The oxygen evolution reaction (OER) plays a pivotal role in diverse renewable energy storage and conversion technologies, including water electrolysis, electrochemical CO 2 reduction, nitrogen fixation, metal‐air batteries. Among various electrolysis techniques, proton exchange membrane (PEM)‐based devices offer numerous advantages, high current densities, exceptional chemical stability, excellent conductivity, high‐purity H . Nevertheless, the prohibitive cost associated with Ir/Ru‐based OER electrocatalysts poses significant barrier to broad‐scale application of PEM‐based splitting. Consequently, it is crucial advance development non‐noble metal catalysis substance acid‐activity thereby fostering their widespread integration into PEM electrolyzers (PEMWEs). In this review, comprehensive analysis acidic mechanism, encompassing adsorbate mechanism (AEM), lattice (LOM) oxide path (OPM) offered. Subsequently, systematic summary recently reported noble‐metal‐free catalysts transition metal‐based, carbon‐based other types provided. Additionally, compilation situ/operando characterization techniques provided, serving as invaluable tools for furnishing experimental evidence comprehend catalytic mechanism. Finally, present challenges future research directions concerning precious‐metal‐free are comprehensively summarized discussed review.

Язык: Английский

---

Bioinspired Binickel Catalyst for Carbon Dioxide Reduction: The Importance of Metal–ligand Cooperation

JACS Au, Год журнала: 2024, Номер 4(3), С. 1207 - 1218

Опубликована: Март 11, 2024

Catalyst design for the efficient CO2 reduction reaction (CO2RR) remains a crucial challenge conversion of to fuels. Natural Ni–Fe carbon monoxide dehydrogenase (NiFe-CODH) achieves reversible and CO at nearly thermodynamic equilibrium potential, which provides template developing CO2RR catalysts. However, compared with natural enzyme, most biomimetic synthetic complexes exhibit negligible catalytic activities, emphasizes significance effective bimetallic cooperation activation. Enlightened by synergy, we herein report dinickel complex, NiIINiII(bphpp)(AcO)2 (where NiNi(bphpp) is derived from H2bphpp = 2,9-bis(5-tert-butyl-2-hydroxy-3-pyridylphenyl)-1,10-phenanthroline) electrocatalytic CO, exhibits remarkable reactivity approximately 5 times higher than that mononuclear Ni catalyst. Electrochemical computational studies have revealed redox-active phenanthroline moiety effectively modulates electron injection transfer akin [Fe3S4] cluster in NiFe-CODH, secondary site facilitates C–O bond activation cleavage through mediation Lewis acid characteristics. Our work underscores significant role catalysis valuable guidance rational

Язык: Английский

---

Metal‐Organic Frameworks: Direct Synthesis by Organic Acid‐Etching and Reconstruction Disclosure as Oxygen Evolution Electrocatalysts

Angewandte Chemie, Год журнала: 2024, Номер 136(11)

Опубликована: Янв. 22, 2024

Abstract Metal‐organic frameworks (MOFs) have emerged as promising oxygen evolution reaction (OER) electrocatalysts. Chemically bonded MOFs on supports are desirable yet lacking in routine synthesis, they may allow variable structural and the underlying structure‐activity relationship to be disclosed. Herein, direct MOF synthesis is achieved by an organic acid‐etching strategy (AES). Using π‐conjugated ferrocene (Fc) dicarboxylic acid etching agent ligand, a series of MFc‐MOF (M=Ni, Co, Fe, Zn) nanosheets synthesized metal supports. The crystal structure studied using X‐ray diffraction low‐dose transmission electron microscopy, which quasi ‐lattice‐matched with that metal, enabling situ growth. Operando Raman attenuated total reflectance Fourier transform infrared spectroscopy disclose NiFc‐MOF features dynamic rebuilding during OER. reconstructed one showing optimized electronic structures upshifted d ‐band center, high M−O bonding state occupancy, localized electrons adsorbates indicated density functional theory calculations, exhibits outstanding OER performance fairly low overpotential (130 mV at 10 mA cm −2 ) good stability (144 h). newly established approach for reconstruction disclosure stimulate development more prudent catalysts advancing

Язык: Английский

---

Pivotal Role of Geometry Regulation on O−O Bond Formation Mechanism of Bimetallic Water Oxidation Catalysts

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(9)

Опубликована: Янв. 5, 2024

Abstract In this study, we highlight the impact of catalyst geometry on formation O−O bonds in Cu 2 and Fe catalysts. A series complexes with diverse linkers are designed as electrocatalysts for water oxidation. Interestingly, catalytic performance these is enhanced their molecular skeletons become more rigid, which contrasts behavior observed our previous investigation analogs. Moreover, mechanistic studies reveal that reactivity bridging O atom results distinct pathways bond systems, coupling takes place between a terminal III −OH μ −O⋅ radical. Whereas it involves two Fe–oxo entities. Furthermore, an in‐depth structure–activity analysis uncovers spatial geometric prerequisites OH radical, ultimately leading to formation. Overall, study emphasizes critical role precisely adjusting catalysts align bonding pathway.

Язык: Английский

---

Uncovering Interfacial Oxygen‐Bridged Binuclear Metal Centers of Heterogenized Molecular Catalyst for Water Electrolysis

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Март 30, 2025

Abstract The success of different heterogeneous strategies organometallic catalysts has been demonstrated to achieve high selectivity and activity in photo/electrocatalysis. However, yielding their catalytic mechanisms at complex molecule‐electrode electrochemical interfaces remains a great challenge. Herein, shell‐isolated nanoparticle‐enhanced Raman spectroscopy is employed elucidate the dynamic process, interfacial structure, intermediates copper hydroxide‐2‐2′ bipyridine on Au electrode ((bpy)Cu(OH) 2 /Au) during oxygen evolution reaction (OER). Direct molecular evidences reveal that (bpy)Cu(OH) oxidizes into Cu(III) bridges atoms via oxygenated species, forming (bpy)Cu(III)O ‐Au with oxygen‐bridged binuclear metal centers Cu(III)‐O‐Au for OER. As potential further increases, combines surface hydroxyl groups (*OH) form important intermediate Cu(III)‐OOH‐Au, which then turns Cu(III)‐OO‐Au release O . Furthermore, situ impedance proves lower resistance faster mass transport hydroxy enhance Theoretical calculations formation significantly modify elementary steps OER, resulting potential‐determining step ≈0.58 V than bare Au. This work provides new insights OER mechanism immobilized‐molecule development application renewable energy conversion devices.

Язык: Английский

---

Designing a Schottky coupled p–n junction to enhance the kinetic behavior of the oxygen evolution reaction

Journal of Materials Chemistry A, Год журнала: 2023, Номер 12(3), С. 1804 - 1815

Опубликована: Дек. 1, 2023

The design of the energy band structure modulates surface charge distribution and optimizes levels Fe 3 C-NG@NiFe, construction double heterojunction introduces additional active sites fast electron transfer for OER.

Язык: Английский

---