While acidic oxygen evolution reaction plays a critical role in electrochemical energy conversion devices, the sluggish reaction kinetics and poor stability in acidic electrolyte challenges materials development. Unlike traditional nano-structuring approaches, this work focuses on the structural symmetry breaking to rearrange spin electron occupation and optimize spin-dependent orbital interaction to alter charge transfer between catalysts and reactants. Herein, we propose an atomic half-disordering strategy in multistage-hybridized BixEr2-xRu2O7 pyrochlores to reconfigure orbital degeneracy and spin-related electron occupation. This strategy involves controlling the bonding interaction of Bi-6s lone pair electrons, in which partial atom rearrangement makes the active sites transform into asymmetric high-spin states from symmetric low-spin states. As a result, the half-disordered BixEr2-xRu2O7 pyrochlores demonstrate an overpotential of ~0.18 V at 10 mA cm-2 accompanied with excellent stability of 100 h in acidic electrolyte. Our findings not only provide a strategy for designing atom-disorder-related catalysts, but also provides a deeper understanding of the spin-related acidic oxygen evolution reaction kinetics.
The development of acid-stable water oxidation electrocatalysts is crucial for high-performance energy conversion devices. Different from traditional nanostructuring, here we employ an innovative microwave-mediated electron–phonon coupling technique to assemble specific Ru atomic patterns (instead of random Ru-particle depositions) on Mn0.99Cr0.01O2 surfaces (RuMW-Mn1-xCrxO2) in RuCl3 solution because hydrated Ru-ion complexes can be uniformly activated to replace some Mn sites at nearby Cr-dopants through microwave-triggered energy coherent superposition with molecular rotations and collisions. This selective rearrangement in RuMW-Mn1-xCrxO2 with particular spin-differentiated polarizations can induce localized spin domain inversion from reversed to parallel direction, which makes RuMW-Mn1-xCrxO2 demonstrate a high current density of 1.0 A cm−2 at 1.88 V and over 300 h of stability in a proton exchange membrane water electrolyzer. The cost per gallon of gasoline equivalent of the hydrogen produced is only 43% of the 2026 target set by the U.S. Department of Energy, underscoring the economic significance of this nanotechnology. The development of acid-stable water oxidation electrocatalysts is crucial for high-performance energy conversion devices. Here, the authors report a microwave-mediated electron–phonon coupling technique for the specific assembly of Ru atoms that enhances spin-sensitive acidic water oxidation.
This work suggests an intriguing light-driven atomic assembly proposal to orderly configure the distribution of reactive sites to optimize the spin-entropy-related orbital interaction and charge transfer from electrocatalysts to intermediates. Herein, the introduced fluorine (F) atoms acting as photo-corrosion centres in MnO1.9 F0.1 effectively soften the bonding interaction of Mn-O bonds in the IrCl3 solution. Therefore, partial Mn atoms can be successively replaced to form orderly atomic-hybridized catalysts with a spin-related low entropy due to the coexistence of Ir-atomic chains and clusters. The time-related elemental analysis demonstrates that the dynamic dissolution/redeposition of Ir clusters in acidic oxygen evolution leads to a reintegration of the reaction pathway to seek the switchable rate-limiting step with a lower activation energy.
Strong p–d intermetallic hybridization was performed to construct an ordered antiperovskite via transient heating strategy, exhibiting high and stable electrochemical activity in both ammonia synthesis and zinc–nitrate battery.
Abstract This work suggests an intriguing light‐driven atomic assembly proposal to orderly configure the distribution of reactive sites to optimize the spin‐entropy‐related orbital interaction and charge transfer from electrocatalysts to intermediates. Herein, the introduced fluorine (F) atoms acting as photo‐corrosion centres in MnO 1.9 F 0.1 effectively soften the bonding interaction of Mn−O bonds in the IrCl 3 solution. Therefore, partial Mn atoms can be successively replaced to form orderly atomic‐hybridized catalysts with a spin‐related low entropy due to the coexistence of Ir‐atomic chains and clusters. The time‐related elemental analysis demonstrates that the dynamic dissolution/redeposition of Ir clusters in acidic oxygen evolution leads to a reintegration of the reaction pathway to seek the switchable rate‐limiting step with a lower activation energy.
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