Striking Stabilization Effect of Spinel Cobalt Oxide Oxygen Evolution Electrocatalysts in Neutral pH by Dual-Sites Iron Incorporation

Developing stable and efficient nonprecious-metal-based oxygen evolution catalysts in the neutral electrolyte is a challenging but essential goal for various electrochemical systems.Particularly,cobalt-based spinels have drawn a considerable amount of attention but most of them operate in alkali solutions.However,the frequently studied Co-Fe spinel system never exhibits appreciable stability in nonbasic conditions,not to mention attract further investigation on its key structural motif and transition states for activity loss.Herein,we report exceptional stable Co-Fe spinel oxygen evolution catalysts(~30%Fe is optimal)in a neutral electrolyte,owing to its unique metal ion arrangements in the crystal lattice.The introduced iron content enters both the octahedral and tetrahedral sites of the spinel as Fe^(2+)and Fe^(3+)(with Co ions having mixed distribution as well).Combining density functional theory calculations,we find that the introduction of Fe to Co_(3)O_(4)lowers the covalency of metal-oxygen bonds and can help suppress the oxidation of Co^(2+/3+)and 0^(2-).It implies that the Co-Fe spinel will have minor surface reconstruction and less lattice oxygen loss during the oxygen evolution reaction process in comparison with Co_(3)O_(4)and hence show much better stability.These findings suggest that there is still much chance for the spinel structures,especially using reasonable sublattices engineering via multimetal doping to develop advanced oxygen evolution catalysts.

Unveiling the intrinsic properties of single NiZnFeO_x entity for promoting electrocatalytic oxygen evolution

Although considerable research efforts have been devoted to the design and development of non-noble electrocatalysts for oxygen evolution reaction(OER), substantial enhancement of OER performance with commercial-scale water electrolysis remains a big challenge. This could result from the difficulties in detecting the intrinsic properties and overlooking the assembly process for electrochemical OER process. Here, we employ a microjet collision method to investigate the intrinsic OER activities of individual NiZnFeO_x entities with and without a moderate magnetic field. Our results demonstrate that single NiZnFeO_x nanoparticles(NPs) show the excellent OER performance with a lowest onset potential(~1.35 V vs. RHE) and a greatest magnetic enhancement(~118%) among bulk materials, single agglomerations and NPs. Furthermore, we explore the utility of theoretical investigation by density functional theory(DFT)calculations for studying OER process on NiZnFeO_x surfaces without and with spin alignment, indicating monodispersed NiZnFeO_xNPs with totally spin alignment facilitates the OER process under the external magnetic field. It is found that the well-dispersion of NiZnFeO_x NPs would increase the electrical conductivity and the surface spin state, resulting in promoting their OER activities. This work provides a test for uncovering the essential roles of NPs assembly to a significant promotion of their magnet-assisted OER.

A trace of Pt can significantly boost RuO_(2) for acidic water splitting

The development of highly potential electrocatalysts for acidic water electrolysis is particularly desirable for many energy‐related processes.Herein,we demonstrated a versatile strategy to activate and stabilize RuO_(2)‐based electrocatalyst for acidic water splitting by a trace of Pt,where Pt plays an essential role in promoting oxygen evolution reaction(OER),and can simultaneously act as the active site for hydrogen evolution reaction(HER).Compared with pure Ru oxide nanosheet assemblies(Ru ONAs),the“5%Pt‐containing”Ru ONAs(5%Pt‐Ru ONAs)achieve much enhanced OER activity in 0.5 and 0.05 mol/L H_(2)SO_(4),with much lower overpotentials of 227 and 234 mV at 10 mA cm^(‒2),respectively.Experimental and theoretical analyses reveal that the atomically dispersed Pt incorporating into RuO_(2)lattice is conducive to increasing the concentration of O vacancies,which effectively enhances the interaction with reaction intermediate and thus lowers the energy barrier for the formation of OOH*.Moreover,benefited from the presence of Pt,the formation of RuO_(2)is more achievable when proper annealing is applied.In addition to OER,due to the presence of active Pt,the HER performance of 5%Pt‐Ru ONAs can also be ensured,thereby realizing efficient acidic overall water splitting.Finally,the excellent activity can also be achieved without sacrificing stability.This work highlights an attractive strategy for designing active and stable RuO_(2)‐based electrocatalysts for acidic overall water splitting.

High-performance bulk heterojunction-based photocathode with facile architecture for photoelectrochemical water splitting

Organic semiconductors are promising candidates as photoactive layers for photoelectrodes used in photoelectrochemical(PEC)cells due to their excellent light absorption and efficient charge transport properties with the help of interfacial materials.However,the use of multilayers will make the charge transfer mechanism more complicated and decrease the PEC performance of the photoelectrode caused by the increased contact resistance.In this work,a PM6:Y6 bulk heterojunction(BHJ)-based photocathode is fabricated for efficient PEC hydrogen evolution reaction(HER)in an acidic aqueous solution.With RuO_(2)as an interfacial modification layer,the photocathode with a simple structure(fluorine-doped tin oxide(FTO)/PM6:Y6/RuO_(2))generates a maximum photocurrent density up to-15 m A/cm^(2)at 0 V vs.reference hydrogen electrode(RHE),outperforming all previously reported BHJ-based photocathodes in terms of PEC performance.The highest ratiometric power-saved efficiency of 3.7%is achieved at 0.4 V vs.RHE.

Atomically isolated Pd sites within Pd-S nanocrystals enable trifunctional catalysis for direct,electrocatalytic and photocatalytic syntheses of H_(2)O_(2)

Although high-efficiency production of hydrogen peroxide(H_(2)O_(2))can be realized separately by means of direct,electrochemical,and photocatalytic synthesis,developing versatile catalysts is particularly challenging yet desirable.Herein,for the first time we reported that palladium-sulphur nanocrystals(Pd-S NCs)can be adopted as robust and universal catalysts,which can realize the efficient O_(2) conversion by three methods.As a result,Pd-S NCs exhibit an excellent selectivity(89.5%)to H_(2)O_(2)with high productivity(133.6 mol·kgcat^(−1)·h^(−1))in the direct synthesis,along with the significantly enhanced H_(2)O_(2)production activity and stability via electrocatalytic and photocatalytic syntheses.It is demonstrated that the isolated Pd sites can enhance the adsorption of O_(2) and inhibit its O–O bond dissociation,improving H_(2)O_(2)selectivity and reducing H_(2)O_(2)degradation.Further study confirms that the difference in surface atom composition and arrangement is the key factor for different ORR mechanisms on Pd NCs and Pd-S NCs.

Face-centered cubic structured RuCu hollow urchin-like nanospheres enable remarkable hydrogen evolution catalysis

Ruthenium(Ru)is one of the most promising metals for its versatility in driving a wide range of catalytic reactions.However,owing to the intrinsic preference of hexagonal close-packed(hcp)phase for bulk Ru,currently,it is still challenging to construct Ru-based nanomaterials with face-centered-cubic(fcc)phase for optimizing their performance towards potential applications.Herein,we report a facile wet-chemical method to directly create unconventional fcc-structured Ru-copper hollow urchin-like nanospheres(fcc-RuCu HUNSs)as a class of efficient pH-universal hydrogen evolution reaction(HER)electrocatalyst.Interestingly,this synthetic strategy can be expanded to prepare other fcc-Ru-based alloy nanomaterials.Significantly,the novel fcc-RuCu HUNSs exhibit superior HER performance with the overpotential of only 25,34,40,and 26 m V to reach the current density of 10 mA cm^(-2)in 0.5 M H_(2)SO_(4),0.05 M H_(2)SO_(4),0.1 M KOH,and 1 M KOH,respectively,much lower than those of hcpRuCu HUNSs and commercial Pt/C.Density functional theory(DFT)calculations further indicate that their excellent pH-universal HER performance results from the optimized adsorption free energy of H and work functions.Our work highlights the importance of phase control to design high-efficiency nanocatalysts for relevant catalytic reactions in energy conversion.