Proton exchange membrane (PEM) water electrolyzers hold great significance for renewable energy storage and conversion. The acidic oxygen evolution reaction (OER) is one of the main roadblocks that ...hinder the practical application of PEM water electrolyzers. Highly active, cost‐effective, and durable electrocatalysts are indispensable for lowering the high kinetic barrier of OER to achieve boosted reaction kinetics. To date, a wide spectrum of advanced electrocatalysts has been designed and synthesized for enhanced acidic OER performance, though Ir and Ru based nanostructures still represent the state‐of‐the‐art catalysts. In this Progress Report, recent research progress in advanced electrocatalysts for improved acidic OER performance is summarized. First, fundamental understanding about acidic OER including reaction mechanisms and atomic understanding to acidic OER for rational design of efficient electrocatalysts are discussed. Thereafter, an overview of the progress in the design and synthesis of advanced acidic OER electrocatalysts is provided in terms of catalyst category, i.e., metallic nanostructures (Ir and Ru based), precious metal oxides, nonprecious metal oxides, and carbon based nanomaterials. Finally, perspectives to the future development of acidic OER are provided from the aspects of reaction mechanism investigation and more efficient electrocatalyst design.
The acidic oxygen evolution reaction is the key to realizing the application of proton‐exchange membrane water electrolyzers. The most recent advances in advanced electrocatalysts for enhancing the acidic oxygen evolution reaction, including Ir‐based, Ru‐based, nonprecious‐metal‐based, and carbon‐based nanostructures, are comprehensively summarized. The strategies summarized are of benefit for more advanced electrocatalysts design.
The development of bimetal based catalysts via interfacial engineered strategy has been intensively explored due to its great potential for enhancing the electrochemical performance. The significant ...progress achieved by the interfacial engineering is mainly derived from its great ability on tuning the intermediate adsorption, controlling the electron and mass transportation, preventing catalysts from serious aggregation, as well as providing advanced promoter for the rational design of highly efficient catalysts. Here, the recent works on the interfacial engineered strategy for developing highly efficient bimetal based electrocatalysts are outlined. The advantages of interfacial engineered strategy on manipulating the activity, selectivity, and stability of catalysts are first discussed. The recent synthetic approaches for controlling the interface structures and the related hydrogen evolution reaction, oxygen evolution reaction, oxygen reduction reaction, and electroreduction of carbon dioxide are elaborated based on three major categories, involving metal/metal, metal/metal compound, and metal/support interfaces. Challenges and perspectives of this field are represented in the final section.
Interfacial engineering of bimetallic nanostructures with enhanced performance has emerged as an important branch in a wide range of electro‐applications. Herein, advances of the interfacial engineered strategies are outlined, including their advantages in manipulating the activity, selectivity, and stability, novel synthetic methods, as well as typical examples for electro‐applications are reviewed. Challenges and perspectives for the advanced electrocatalysts are finally presented.
Channel‐rich RuCu snowflake‐like nanosheets (NSs) composed of crystallized Ru and amorphous Cu were used as efficient electrocatalysts for oxygen evolution reaction (OER), hydrogen evolution reaction ...(HER), and overall water splitting in pH‐universal electrolytes. The optimized RuCu NSs/C‐350 °C and RuCu NSs/C‐250 °C show attractive activities of OER and HER with low overpotentials and small Tafel slopes, respectively. When applied to overall water splitting, the optimized RuCu NSs/C can reach 10 mA cm−2 at cell voltages of only 1.49, 1.55, 1.49 and 1.50 V in 1 m KOH, 0.1 m KOH, 0.5 m H2SO4 and 0.05 m H2SO4, respectively, much lower than those of commercial Ir/C∥Pt/C. The optimized electrolyzer exhibits superior durability with small potential change after up to 45 h in 1 m KOH, showing a class of efficient functional electrocatalysts for overall water splitting.
Channel rich RuCu nanosheets (NSs) have been successfully prepared and applied as a highly active and stable bifunctional electrocatalyst for the oxygen evolution reaction, hydrogen evolution reaction, as well as overall water splitting. This system is one of the best electrocatalysts reported to date.
Shape-controlled noble metal nanocrystals (NCs), such as Au, Ag, Pt, Pd, Ru, and Rh are of great success due to their new and enhanced properties and applications in chemical conversion, fuel cells, ...and sensors, but the realization of shape control of Ir NCs for achieving enhanced electrocatalysis remains a significant challenge. Herein, we report an efficient solution method for a new class of three-dimensional (3D) Ir superstructure that consists of ultrathin Ir nanosheets as subunits. Electrochemical studies show that it delivers the excellent electrocatalytic activity toward oxygen evolution reaction (OER) in alkaline condition with an onset potential at 1.43 V versus reversible hydrogen electrode (RHE) and a very low Tafel slope of 32.7 mV decade–1. In particular, it even shows superior performance for OER in acidic solutions with the low onset overpotential of 1.45 V versus RHE and small Tafel slope of 40.8 mV decade–1, which are much better than those of small Ir nanoparticles (NPs). The 3D Ir superstructures also exhibit good stability under acidic condition with the potential shift of less than 20 mV after 8 h i-t test. The present work highlights the importance of tuning 3D structures of Ir NCs for enhancing OER performance.
Pursuing active and durable water splitting electrocatalysts is of vital significance for solving the sluggish kinetics of the oxygen evolution reaction (OER) process in energy supply. Herein, ...theoretical calculations identify that the local distortion-strain effect in amorphous RuTe
system abnormally sensitizes the Te-pπ coupling capability and enhances the electron-transfer of Ru-sites, in which the excellent inter-orbital p-d transfers determine strong electronic activities for boosting OER performance. Thus, a robust electrocatalyst based on amorphous RuTe
porous nanorods (PNRs) is successfully fabricated. In the acidic water splitting, a-RuTe
PNRs exhibit a superior performance, which only require a cell voltage of 1.52 V to reach a current density of 10 mA cm
. Detailed investigations show that the high density of defects combine with oxygen atoms to form RuO
H
species, which are conducive to the OER. This work offers valuable insights for constructing robust electrocatalysts based on theoretical calculations guided by rational design and amorphous materials.
Carbon dioxide (CO2) hydrogenation to ethanol (C2H5OH) is considered a promising way for CO2 conversion and utilization, whereas desirable conversion efficiency remains a challenge. Herein, highly ...active, selective and stable CO2 hydrogenation to C2H5OH was enabled by highly ordered Pd-Cu nanoparticles (NPs). By tuning the composition of the Pd-Cu NPs and catalyst supports, the efficiency of CO2 hydrogenation to C2H5OH was well optimized with Pd2Cu NPs/P25 exhibiting high selectivity to C2H5OH of up to 92.0% and the highest turnover frequency of 359.0 h–1. Diffuse reflectance infrared Fourier transform spectroscopy results revealed the high C2H5OH production and selectivity of Pd2Cu NPs/P25 can be ascribed to boosting *CO (adsorption CO) hydrogenation to *HCO, the rate-determining step for the CO2 hydrogenation to C2H5OH.
Functionalized graphene hydrogels are prepared by a one‐step low‐temperature reduction process and exhibit ultrahigh specific capacitances and excellent cycling stability in the aqueous electrolyte. ...Flexible solid‐state supercapacitors based on functionalized graphene hydrogels are demonstrated with superior capacitive performances and extraordinary mechanical flexibility.
The anodic oxygen evolution reaction (OER) is central to various energy conversion devices, but the investigation of the dynamic evolution of catalysts in different OER conditions remains quite ...limited, which is unfavorable for the understanding of the actual structure–activity relationship and catalyst optimization. Herein, we constructed monodispersed IrNi x nanoparticles (NPs) with distinct composition-segregated features and captured their structural evolution in various OER environments. We decoded the interesting self-reconstruction of IrNi x NPs during the OER, in which an Ir-skin framework is generated in an acidic electrolyte, while a Ni-rich surface layer is observed in an alkaline electrolyte owing to Ni migration. Benefiting from such self-reconstruction, considerable OER enhancements are achieved under both acidic and alkaline conditions. For comparison, IrNi x nanoframes with Ir skins prepared by chemical etching show a similar structural evolution result in the acidic electrolyte, but a total different phenomenon in the alkaline electrolyte. By tracking the structural evolution of IrNi x catalysts and correlating them with OER activity trajectories, the present work provides a significant understanding for designing efficient OER catalysts with controlled compositional distributions.
The selective hydrogenation of α, β-unsaturated aldehyde is an extremely important transformation, while developing efficient catalysts with desirable selectivity to highly value-added products is ...challenging, mainly due to the coexistence of two conjugated unsaturated functional groups. Herein, we report that a series of Pt-based zigzag nanowires (ZNWs) can be adopted as selectivity controllers for α, β-unsaturated aldehyde hydrogenation, where the excellent unsaturated alcohol (UOL) selectivity (>95%) and high saturated aldehyde (SA) selectivity (>94%) are achieved on PtFe ZNWs and PtFeNi ZNWs+AlCl3, respectively. The excellent UOL selectivity of PtFe ZNWs is attributed to the lower electron density of the surface Pt atoms, while the high SA selectivity of PtFeNi ZNWs+AlCl3 is due to synergy between PtFeNi ZNWs and AlCl3, highlighting the importance of Pt-based NWs with precisely controlled surface and composition for catalysis and beyond.
Abstract
Electroreduction of carbon dioxide (CO
2
) into multicarbon products provides possibility of large-scale chemicals production and is therefore of significant research and commercial ...interest. However, the production efficiency for ethanol (EtOH), a significant chemical feedstock, is impractically low because of limited selectivity, especially under high current operation. Here we report a new silver–modified copper–oxide catalyst (dCu
2
O/Ag
2.3%
) that exhibits a significant Faradaic efficiency of 40.8% and energy efficiency of 22.3% for boosted EtOH production. Importantly, it achieves CO
2
–to–ethanol conversion under high current operation with partial current density of 326.4 mA cm
−2
at −0.87 V vs reversible hydrogen electrode to rank highly significantly amongst reported Cu–based catalysts. Based on in situ spectra studies we show that significantly boosted production results from tailored introduction of Ag to optimize the coordinated number and oxide state of surface Cu sites, in which the
*
CO adsorption is steered as both atop and bridge configuration to trigger asymmetric C–C coupling for stablization of EtOH intermediates.
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