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1.
Angew Chem Int Ed Engl ; : e202411125, 2024 Sep 14.
Artículo en Inglés | MEDLINE | ID: mdl-39276024

RESUMEN

Topological defects are inevitable existence in carbon-based frameworks, but their intrinsic electrocatalytic activity and mechanism remain under-explored. Herein, the hydrogen evolution reaction (HER) of pentagonal carbon-rings is probed by constructing pentagonal ring-rich carbon (PRC), with optimized electronic structures and higher HER activity relative to common hexagonal carbon (HC). Furthermore, to improve the reactivity, we couple Ru clusters with PRC (Ru@PRC) through p-d orbital hybridization between C and Ru atoms, which drives a shortcut transfer of electrons from Ru clusters to pentagonal rings. The electron-deficient Ru species leads to a notable negative shift in d-band centers of Ru and weakens their binding strength with hydrogen intermediates, thus enhancing the HER activity in different pH media. Especially, at a current density of 10 mA cm-2, PRC greatly reduces alkaline HER overpotentials from 540 to 380 mV. And Ru@PRC even exhibits low overpotentials of 28 and 275 mV to reach current densities of 10 and 1000 mA cm-2, respectively. Impressively, the mass activity and price activity of Ru@PRC are 7.83 and 15.7 times higher than that of Pt/C at the overpotential of 50 mV. Our data unveil the positive HER reactivity of pentagonal defects and good application prospects.

2.
Chem Sci ; 2024 Sep 13.
Artículo en Inglés | MEDLINE | ID: mdl-39328191

RESUMEN

The electronic structure modulation through heterogeneous single-atom doping is an effective strategy to improve electrocatalysis performance of catalysts. Here, Ir single-atom doped RuO2 (IrSA/RuO2) is constructed by substituting Ru sites with mono-disperse Ir atoms in RuO2 crystals. The IrSA/RuO2-850 catalyst shows excellent activity for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline media, with overpotentials of only 37 and 234 mV respectively, at a current density of 10 mA cm-2, lower than that of commercial Pt/C (39 mV-HER) and RuO2 (295 mV-OER). Notably, no significant degradation occurs during the 1000 h HER stability test at 500 mA cm-2. Furthermore, IrSA/RuO2-850 also demonstrates superior catalytic activity and stability in acidic media. Theoretical calculations show that the interaction between Ir and RuO2 modulates the electronic structure of both Ru and Ir sites, resulting in the lowest reaction energy barriers of Ru and Ir sites for the HER and OER, respectively, which thermodynamically explains the enhancement of the catalytic activity. Besides, the introduction of Ir atoms also enhances the demetallation energy of Ru atoms and strengthens the structural stability of the crystal, leading to the improved stability of the catalyst. This work provides an effective strategy for construction of high-performing catalysts by precisely controlling the electronic structure and active sites of polymetal atoms.

3.
Nat Commun ; 15(1): 8293, 2024 Sep 27.
Artículo en Inglés | MEDLINE | ID: mdl-39333518

RESUMEN

Simultaneously activating metal and lattice oxygen sites to construct a compatible multi-mechanism catalysis is expected for the oxygen evolution reaction (OER) by providing highly available active sites and mediate catalytic activity/stability, but significant challenges remain. Herein, Fe and S dually modulated NiFe oxyhydroxide (R-NiFeOOH@SO4) is conceived by complete reconstruction of NiMoO4·xH2O@Fe,S during OER, and achieves compatible adsorbate evolution mechanism and lattice oxygen oxidation mechanism with simultaneously optimized metal/oxygen sites, as substantiated by in situ spectroscopy/mass spectrometry and chemical probe. Further theoretical analyses reveal that Fe promotes the OER kinetics under adsorbate evolution mechanism, while S excites the lattice oxygen activity under lattice oxygen oxidation mechanism, featuring upshifted O 2p band centers, enlarged d-d Coulomb interaction, weakened metal-oxygen bond and optimized intermediate adsorption free energy. Benefiting from the compatible multi-mechanism, R-NiFeOOH@SO4 only requires overpotentials of 251 ± 5/291 ± 1 mV to drive current densities of 100/500 mA cm-2 in alkaline media, with robust stability for over 300 h. This work provides insights in understanding the OER mechanism to better design high-performance OER catalysts.

4.
Adv Mater ; : e2408285, 2024 Sep 09.
Artículo en Inglés | MEDLINE | ID: mdl-39246151

RESUMEN

A breakthrough in manufacturing procedures often enables people to obtain the desired functional materials. For the field of energy conversion, designing and constructing catalysts with high cost-effectiveness is urgently needed for commercial requirements. Herein, the molten salt-assisted synthesis (MSAS) strategy is emphasized, which combines the advantages of traditional solid and liquid phase synthesis of catalysts. It not only provides sufficient kinetic accessibility, but effectively controls the size, morphology, and crystal plane features of the product, thus possessing promising application prospects. Specifically, the selection and role of the molten salt system, as well as the mechanism of molten salt assistance are analyzed in depth. Then, the creation of the catalyst by the MSAS and the electrochemical energy conversion related application are introduced in detail. Finally, the key problems and countermeasures faced in breakthroughs are discussed and look forward to the future. Undoubtedly, this systematical review and insights here will promote the comprehensive understanding of the MSAS and further stimulate the generation of new and high efficiency catalysts.

5.
Nat Commun ; 15(1): 7371, 2024 Aug 27.
Artículo en Inglés | MEDLINE | ID: mdl-39191739

RESUMEN

Fast-charging, non-aqueous lithium-based batteries are desired for practical applications. In this regard, LiMn2O4 is considered an appealing positive electrode active material because of its favourable ionic diffusivity due to the presence of three-dimensional Li-ion diffusion channels. However, LiMn2O4 exhibits inadequate rate capabilities and rapid structural degradation at high currents. To circumvent these issues, here we introduce quintuple low-valence cations to increase the entropy of LiMn2O4. As a result, the entropy-increased LiMn2O4-based material, i.e., LiMn1.9Cu0.02Mg0.02Fe0.02Zn0.02Ni0.02O4, when tested in non-aqueous lithium metal coin cell configuration, enable 1000 cell cycles at 1.48 A g-1 (corresponding to a cell charging time of 4 minutes) and 25°C with a discharge capacity retention of about 80%. We demonstrate that the increased entropy in LiMn2O4 leads to an increase in the disordering of dopant cations and a contracted local structure, where the enlarged LiO4 space and enhanced Mn-O covalency improve the Li-ion transport and stabilize the diffusion channels. We also prove that stress caused by cycling at a high cell state of charge is relieved through elastic deformation via a solid-solution transition, thus avoiding structural degradation upon prolonged cycling.

6.
Small ; : e2405399, 2024 Aug 25.
Artículo en Inglés | MEDLINE | ID: mdl-39183523

RESUMEN

The oxygen evolution reaction (OER) plays a pivotal role in diverse renewable energy storage and conversion technologies, including water electrolysis, electrochemical CO2 reduction, nitrogen fixation, and metal-air batteries. Among various water electrolysis techniques, proton exchange membrane (PEM)-based water electrolysis devices offer numerous advantages, including high current densities, exceptional chemical stability, excellent proton conductivity, and high-purity H2. Nevertheless, the prohibitive cost associated with Ir/Ru-based OER electrocatalysts poses a significant barrier to the broad-scale application of PEM-based water splitting. Consequently, it is crucial to advance the development of non-noble metal OER catalysis substance with high acid-activity and stability, thereby fostering their widespread integration into PEM water electrolyzers (PEMWEs). In this review, a comprehensive analysis of the acidic OER mechanism, encompassing the adsorbate evolution mechanism (AEM), lattice oxygen mechanism (LOM) and oxide path mechanism (OPM) is offered. Subsequently, a systematic summary of recently reported noble-metal-free catalysts including transition metal-based, carbon-based and other types of catalysts is provided. Additionally, a comprehensive compilation of in situ/operando characterization techniques is provided, serving as invaluable tools for furnishing experimental evidence to comprehend the catalytic mechanism. Finally, the present challenges and future research directions concerning precious-metal-free acidic OER are comprehensively summarized and discussed in this review.

7.
Small ; : e2406105, 2024 Aug 30.
Artículo en Inglés | MEDLINE | ID: mdl-39212643

RESUMEN

Avoiding the stacking of active sites in catalyst structural design is a promising route for realizing active oxygen evolution reaction (OER). Herein, using a CoFe Prussian blue analoge cube with hollow structure (C-CoFe PBA) as a derived support, a highly effective Ni2P-FeP4-Co2P catalyst with a larger specific surface area is reported. Benefiting from the abundant active sites and fast charge transfer capability of the phosphide nanosheets, the Ni2P-FeP4-Co2P catalyst in 1 m KOH requires only overpotentials of 248 and 277 mV to reach current density of 10 and 50 mA cm-2 and outperforms the commercial catalyst RuO2 and most reported non-noble metal OER catalysts. In addition, the two-electrode system consisting of Ni2P-FeP4-Co2P and Pt/C is able to achieve a current density of 10 and 50 mA cm-2 at 1.529 and 1.65 V. This work provides more ideas and directions for synthesizing transition metal catalysts for efficient OER performance.

8.
Angew Chem Int Ed Engl ; 63(35): e202407577, 2024 Aug 26.
Artículo en Inglés | MEDLINE | ID: mdl-38771672

RESUMEN

Interstitial filling of light atoms strongly affects the electronic structure and adsorption properties of the parent catalyst due to ligand and ensemble effects. Different from the conventional doping and surface modification, constructing ordered intermetallic structures is more promising to overcome the dissolution and reconstruction of active sites through strong interactions generated by atomic periodic arrangement, achieving joint improvement in catalytic activity and stability. However, for tightly arranged metal lattices, such as iridium (Ir), obtaining ordered filling atoms and further unveiling their interstitial effects are still limited by highly activated processes. Herein, we report a high-temperature molten salt assisted strategy to form the intermetallic Ir-B compounds (IrB1.1) with ordered filling by light boron (B) atoms. The B residing in the interstitial lattice of Ir constitutes favorable adsorption surfaces through a donor-acceptor architecture, which has an optimal free energy uphill in rate-determining step (RDS) of oxygen evolution reaction (OER), resulting in enhanced activity. Meanwhile, the strong coupling of Ir-B structural units suppresses the demetallation and reconstruction behavior of Ir, ensuring catalytic stability. Such B-induced interstitial effects endow IrB1.1 with higher OER performance than commercial IrO2, which is further validated in proton exchange membrane water electrolyzers (PEMWEs).

9.
Chem Sci ; 15(19): 7259-7268, 2024 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-38756823

RESUMEN

For Fe-NC systems, high-density Fe-N sites are the basis for high-efficiency oxygen reduction reaction (ORR), and P doping can further lower the reaction energy barrier, especially in the form of metal-P bonding. However, limited to the irregular agglomeration of metal atoms at high temperatures, Fe-P bonds and high-density Fe-N cannot be guaranteed simultaneously. Here, to escape the random and violent agglomeration of Fe species during high-temperature carbonization, triphenylphosphine and 2-methylimidazole with a strong metal coordination capability are introduced together to confine Fe growth. With the aid of such bidirectional coordination, the high-density Fe-N site with Fe-P bonds is realized by in situ phosphorylation of Fe in an Fe-NC system (Fe-P-NC) at high temperatures. Impressively, the content of single-atomically dispersed Fe sites for Fe-P-NC dramatically increases from 2.8% to 65.3% compared with that of pure Fe-NC, greatly improving the ORR activity in acidic and alkaline electrolytes. The theoretical calculation results show that the generated Fe2P can simultaneously facilitate the adsorption of intermediates to Fe-N4 sites and the electron transfer, thereby reducing the reaction energy barrier and obtaining superior ORR activity.

10.
Nat Commun ; 15(1): 3928, 2024 May 09.
Artículo en Inglés | MEDLINE | ID: mdl-38724489

RESUMEN

Improving activity and stability of Ruthenium (Ru)-based catalysts in acidic environments is eager to replace more expensive Iridium (Ir)-based materials as practical anode catalyst for proton-exchange membrane water electrolyzers (PEMWEs). Here, a bicontinuous nanoreactor composed of multiscale defective RuO2 nanomonomers (MD-RuO2-BN) is conceived and confirmed by three-dimensional tomograph reconstruction technology. The unique bicontinuous nanoreactor structure provides abundant active sites and rapid mass transfer capability through a cavity confinement effect. Besides, existing vacancies and grain boundaries endow MD-RuO2-BN with generous low-coordination Ru atoms and weakened Ru-O interaction, inhibiting the oxidation of lattice oxygen and dissolution of high-valence Ru. Consequently, in acidic media, the electron- and micro-structure synchronously optimized MD-RuO2-BN achieves hyper water oxidation activity (196 mV @ 10 mA cm-2) and an ultralow degradation rate of 1.2 mV h-1. A homemade PEMWE using MD-RuO2-BN as anode also conveys high water splitting performance (1.64 V @ 1 A cm-2). Theoretical calculations and in-situ Raman spectra further unveil the electronic structure of MD-RuO2-BN and the mechanism of water oxidation processes, rationalizing the enhanced performance by the synergistic effect of multiscale defects and protected active Ru sites.

11.
J Colloid Interface Sci ; 669: 265-274, 2024 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-38718580

RESUMEN

HYPOTHESIS: Metal-organic frameworks (MOFs) are highly suitable precursors for supercapacitor electrode materials owing to their high porosity and stable backbone structures that offer several advantages for redox reactions and rapid ion transport. EXPERIMENTS: In this study, a carbon-coated Ni9S8 composite (Ni9S8@C-5) was prepared via sulfuration at 500 ℃ using a spherical Ni-MOF as the sacrificial template. FINDING: The stable carbon skeleton derived from Ni-MOF and positive structure-activity relationship due to the multinuclear Ni9S8 components resulted in a specific capacity of 278.06 mAh·g-1 at 1 A·g-1. Additionally, the hybrid supercapacitor (HSC) constructed using Ni9S8@C-5 as the positive electrode and the laboratory-prepared coal pitch-based activated carbon (CTP-AC) as the negative electrode achieved an energy density of 69.32 Wh·kg-1 at a power density of 800.06 W·kg-1, and capacity retention of 83.06 % after 5000 cycles of charging and discharging at 5 A·g-1. The Ni-MOF sacrificial template method proposed in this study effectively addresses the challenges associated with structural collapse and agglomeration of Ni9S8 during electrochemical reactions, thus improving its electrochemical performance. Hence, a simple preparation method is demonstrated, with broad application prospects in supercapacitor electrodes.

12.
Angew Chem Int Ed Engl ; 63(12): e202319618, 2024 Mar 18.
Artículo en Inglés | MEDLINE | ID: mdl-38286759

RESUMEN

Efficient dual-single-atom catalysts are crucial for enhancing atomic efficiency and promoting the commercialization of fuel cells, but addressing the sluggish kinetics of hydrogen oxidation reaction (HOR) in alkaline media and the facile dual-single-atom site generation remains formidable challenges. Here, we break the local symmetry of ultra-small ruthenium (Ru) nanoparticles by embedding cobalt (Co) single atoms, which results in the release of Ru single atoms from Ru nanoparticles on reduced graphene oxide (Co1 Ru1,n /rGO). In situ operando spectroscopy and theoretical calculations reveal that the oxygen-affine Co atom disrupts the symmetry of ultra-small Ru nanoparticles, resulting in parasitic Ru and Co dual-single-atom within Ru nanoparticles. The interaction between Ru single atoms and nanoparticles forms effective active centers. The parasitism of Co atoms modulates the adsorption of OH intermediates on Ru active sites, accelerating HOR kinetics through faster formation of *H2 O. As anticipated, Co1 Ru1,n /rGO exhibits ultrahigh mass activity (7.68 A mgRu -1 ) at 50 mV and exchange current density (0.68 mA cm-2 ), which are 6 and 7 times higher than those of Ru/rGO, respectively. Notably, it also displays exceptional durability surpassing that of commercial Pt catalysts. This investigation provides valuable insights into hybrid multi-single-atom and metal nanoparticle catalysis.

13.
Nano Lett ; 24(3): 1015-1023, 2024 Jan 24.
Artículo en Inglés | MEDLINE | ID: mdl-38215497

RESUMEN

Ru-related catalysts have shown excellent performance for the hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR); however, a deep understanding of Ru-active sites on a nanoscale heterogeneous support for hydrogen catalysis is still lacking. Herein, a click chemistry strategy is proposed to design Ru cluster-decorated nanometer RuxFe3-xO4 heterointerfaces (Ru/RuxFe3-xO4) as highly effective bifunctional hydrogen catalysts. It is found that introducing Ru into nanometric Fe3O4 species breaks the symmetry configuration and optimizes the active site in Ru/RuxFe3-xO4 for HER and HOR. As expected, the catalyst displays prominent alkaline HER and HOR performance with mass activity much higher than that of commercial Pt/C as well as robust stability during catalysis because of the strong interaction between the Ru cluster and the RuxFe3-xO4 support, and the optimized adsorption intermediate (Had and OHad). This work sheds light on a promsing approach to improving the electrocatalysis performance of catalysts by the breaking of atomic dimension symmetry.

14.
Adv Mater ; 36(2): e2310699, 2024 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-37967925

RESUMEN

Correlated single-atom catalysts (c-SACs) with tailored intersite metal-metal interactions are superior to conventional catalysts with isolated metal sites. However, precise quantification of the single-atomic interdistance (SAD) in c-SACs is not yet achieved, which is essential for a crucial understanding and remarkable improvement of the correlated metal-site-governed catalytic reaction kinetics. Here, three Ru c-SACs are fabricated with precise SAD using a planar organometallic molecular design and π-π molecule-carbon nanotube confinement. This strategy results in graded SAD from 2.4 to 9.3 Å in the Ru c-SACs, wherein tailoring the Ru SAD into 7.0 Å generates an exceptionally high turnover frequency of 17.92 H2 s-1 and a remarkable mass activity of 100.4 A mg-1 under 50 and 100 mV overpotentials, respectively, which is superior to all the Ru-based catalysts reported previously. Furthermore, density functional theory calculations confirm that Ru SAD has a negative correlation with its d-band center owing to the long-range interactions induced by distinct local atomic geometries, resulting in an appropriate electrostatic potential and the highest catalytic activity on c-SACs with 7.0 Å Ru SAD. The present study promises an attractive methodology for experimentally quantifying the metal SAD to provide valuable insights into the catalytic mechanism of c-SACs.

15.
Adv Sci (Weinh) ; 10(35): e2304179, 2023 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-37880875

RESUMEN

Developing cost-efficient bifunctional water splitting catalysts is crucial for sustainable hydrogen energy applications. Herein, ruthenium (Ru)-incorporated and phosphorus (P)-doped nickel molybdate (Ru-NiMoO(P)4 ) nanosheet array catalysts are synthesized. Due to the synergy of Ru clusters and NiMoO(P)4 by the modulated electronic structure and the rich active sites, impressively, Ru-NiMoO(P)4 exhibits superior OER (194 mV @ 50 mA cm-2 ) and HER (24 mV @ 10 mA cm-2 ) activity in alkaline media, far exceeding that of commercial Pt/C and RuO2 catalysts. Meanwhile, as bifunctional catalyst, to drive the overall water splitting at the current density of 10 mA cm-2 , Ru-NiMoO(P)4 requires only 1.45 V and maintaining stable output for 100 h. Furthermore, Ru-NiMoO(P)4 also possesses excellent capability for seawater electrolysis hydrogen production. Moreover, the successful demonstration of wind and solar hydrogen production systems provide the feasibility of the ultra-low Ru loading catalyst for large-scale hydrogen production in the future.

16.
Inorg Chem ; 62(30): 12079-12088, 2023 Jul 31.
Artículo en Inglés | MEDLINE | ID: mdl-37471651

RESUMEN

Due to the higher energy density, high thermal stability, and low cost, LiNi0.5Mn1.5O4 (LNMO) spinel, with a large voltage operating window, has been one of the most promising cathode materials for lithium-ion batteries (LIBs). However, the interfacial reaction between the cathode and electrolyte and the two-phase reaction within the bulk of LNMO would destroy the original structure and lead to capacity deterioration, posing a significant challenge. Therefore, the way to suppress the transition-metal (TM) dissolution in LNMO has attracted much attention. However, the ordered/disordered phase regulation by metal atom doping to prohibit TM dissolution has not been extensively explored. Herein, a Ge-doping strategy is proposed to adjust the ratio of disordered/ordered phases in LNMO, resulting in exceptional structural stability. For the modified spinel cathode, there is almost no voltage drop and the capacity retention is up to 92.2% over 1000 cycles at 1C. These results demonstrate that incorporating Ge into LNMO forms a robust structure that effectively increases the amount of Mn4+ while blocking the diffusion of TM ions. In addition, Ge-doping also protects the bulk from further reactions with electrolytes, significantly enhancing the interfacial stability and relieving voltage decay in cycling. This approach can also be applied to design other high-stability cathodes through ordered/disordered phase regulation.

17.
Nanomicro Lett ; 15(1): 168, 2023 Jul 03.
Artículo en Inglés | MEDLINE | ID: mdl-37395826

RESUMEN

Precisely tuning the spacing of the active centers on the atomic scale is of great significance to improve the catalytic activity and deepen the understanding of the catalytic mechanism, but still remains a challenge. Here, we develop a strategy to dilute catalytically active metal interatomic spacing (dM-M) with light atoms and discover the unusual adsorption patterns. For example, by elevating the content of boron as interstitial atoms, the atomic spacing of osmium (dOs-Os) gradually increases from 2.73 to 2.96 Å. More importantly, we find that, with the increase in dOs-Os, the hydrogen adsorption-distance relationship is reversed via downshifting d-band states, which breaks the traditional cognition, thereby optimizing the H adsorption and H2O dissociation on the electrode surface during the catalytic process; this finally leads to a nearly linear increase in hydrogen evolution reaction activity. Namely, the maximum dOs-Os of 2.96 Å presents the optimal HER activity (8 mV @ 10 mA cm-2) in alkaline media as well as suppressed O adsorption and thus promoted stability. It is believed that this novel atomic-level distance modulation strategy of catalytic sites and the reversed hydrogen adsorption-distance relationship can shew new insights for optimal design of highly efficient catalysts.

18.
Adv Sci (Weinh) ; 10(25): e2302930, 2023 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-37382393

RESUMEN

To date, precisely tailoring local active sites of well-defined earth-abundant metal-free carbon-based electrocatalysts for attractive electrocatalytic oxygen reduction reaction (ORR), remains challenging. Herein, the authors successfully introduce a strain effect on active C-C bonds adjacent to edged graphitic nitrogen (N), which raises appropriate spin-polarization and charge density of carbon active sites and kinetically favor the facilitation of O2 adsorption and the activation of O-containing intermediates. Thus, the constructed metal-free carbon nanoribbons (CNRs-C) with high-curved edges exhibit outstanding ORR activity with half-wave potentials of 0.78 and 0.9 V in 0.5 m H2 SO4 and 0.1 m KOH, respectively, overwhelming the planar one (0.52 and 0.81 V) and the N-doped carbon sheet (0.41 and 0.71 V). Especially in acidic media, the kinetic current density (Jk ) is 18 times higher than that of the planar one and the N-doped carbon sheet. Notably, these findings show the spin polarization of the asymmetric structure by introducing a strain effect on the C-C bonds for boosting ORR.

19.
Small ; 19(36): e2300030, 2023 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-37144430

RESUMEN

Water electrolysis is an ideal method for industrial green hydrogen production. However, due to increasing scarcity of freshwater, it is inevitable to develop advanced catalysts for electrolyzing seawater especially at large current density. This work reports a unique Ru nanocrystal coupled amorphous-crystal Ni(Fe)P2 nanosheet bifunctional catalyst (Ru-Ni(Fe)P2 /NF), caused by partial substitution of Fe to Ni atoms in Ni(Fe)P2 , and explores its electrocatalytic mechanism by density functional theory (DFT) calculations. Owing to high electrical conductivity of crystalline phases, unsaturated coordination of amorphous phases, and couple of Ru species, Ru-Ni(Fe)P2 /NF only requires overpotentials of 375/295 and 520/361 mV to drive a large current density of 1 A cm-2 for oxygen/hydrogen evolution reaction (OER/HER) in alkaline water/seawater, respectively, significantly outperforming commercial Pt/C/NF and RuO2 /NF catalysts. In addition, it maintains stable performance at large current density of 1 A cm-2 and 600 mA cm-2 for 50 h in alkaline water and seawater, respectively. This work provides a new way for design of catalysts toward industrial-level seawater splitting.

20.
Adv Sci (Weinh) ; 10(18): e2300342, 2023 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-37092569

RESUMEN

Benefitting from the maximum atom utilization efficiency, special size quantum effects and tailored active sites, single-atom catalysts (SACs) have been promising candidates for bifunctional catalysts toward water splitting. Besides, due to the unique structure and properties, some amorphous materials have been found to possess better performance than their crystalline counterparts in electrocatalytic water splitting. Herein, by combining the advantages of ruthenium (Ru) single atoms and amorphous substrates, amorphous molybdenum-based oxide stabilized single-atomic-site Ru (Ru SAs-MoO3- x /NF) catalysts are conceived as a self-supported electrode. By virtue of the large surface area, enhanced intrinsic activity and fast reaction kinetics, the as-prepared Ru SAs-MoO3- x /NF electrode effectively drives both oxygen evolution reaction (209 mV @ 10 mA cm-2 ) and hydrogen evolution reaction (36 mV @ 10 mA cm-2 ) in alkaline media. Impressively, the assembled electrolyzer merely requires an ultralow cell voltage of 1.487 V to deliver the current density of 10 mA cm-2 . Furthermore, such an electrode also exhibits a great application potential in alkaline seawater electrolysis, achieving a current density of 100 mA cm-2 at a low cell voltage of 1.759 V. In addition, Ru SAs-MoO3- x /NF only has very small current density decay in the long-term constant current water splitting test.


Asunto(s)
Rutenio , Agua , Agua de Mar , Óxidos , Electrodos
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