Synthesis of Solvent-Mediated Morphology-Controlled PdSn Alloy Nanocatalysts and their Application in Electrocatalysis of Ethylene Glycol and Ethanol.

2D nanodendrites (NDs) and nanosheets (NSs) have been regarded as efficient nanocatalysts for enhancing the electrocatalytic performance due to their low coordinated sites and abundant electrocatalytic centers. Nevertheless, it remains challenging to construct advanced NDs and NSs in a single reaction system. Herein, by tuning the volume ratios of mixed solvents, the reduction and diffusion rate of Sn2+ on Pd NSs template was rationally controlled to prepare PdSn NDs and PdSn NSs. Ascribed to the open 2D nanostructure, high specific surface area, and robust synergistic effect, the as-prepared PdSn NDs and PdSn NSs exhibited distinguished electrocatalytic activities for ethylene glycol oxidation reaction (EGOR) and ethanol oxidation reaction (EOR), as well as commendable electrocatalytic durability, which were far superior to the Pd NSs and commercial Pd/C. In addition, the PdSn NDs exhibited enhanced reaction kinetics because the characteristic branch structure exposed a high density of active sites. This work may provide significant guidance for preparing excellent nanocatalysts with various morphological features by simply optimizing the content of the coexisting solvents.

In Situ Electrodeposition of Ultralow Pt into NiFe-Metal-Organic Framework/Nickel Foam Nanosheet Arrays as a Bifunctional Catalyst for Overall Water Splitting.

Exploring highly effective bifunctional electrocatalysts with surface structural advantages and synergistic optimization effects among multimetals is greatly important for overall water splitting. Herein, we successfully synthesized Pt-loaded NiFe-metal-organic framework nanosheet arrays grown on nickel foam (Pt-NiFe-MOF/NF) via a facile hydrothermal-electrodeposition process. Benefiting from large exposed specific surface, optimal electrical conductivity and efficient metal-support interaction endow Pt-NiFe-MOF/NF with highly catalytic performance, exhibiting small overpotential of 261 mV toward oxygen evolution reaction and 125 mV toward hydrogen evolution reaction at a current density of 100 mA cm-2 in alkaline medium. More significantly, the assembled water electrolyzer comprising the Pt-NiFe-MOF/NF//Pt-NiFe-MOF/NF couple demands a low cell voltage of 1.45 V to reach 10 mA cm-2. This work renders a viable approach to design dual-functional electrocatalysts with exceptional electrocatalytic activity and stability at high current density, showing the great prospect of water electrolysis for commercial application.

Recent progress of Ni-based nanomaterials for the electrocatalytic oxygen evolution reaction at large current density.

The precise design and development of high-performing oxygen evolution reaction (OER) for the production of industrial hydrogen gas through water electrolysis has been a widely studied topic. A profound understanding of the nature of electrocatalytic processes reveals that Ni-based catalysts are highly active toward OER that can stably operate at a high current density for a long period of time. Given the current gap between research and applications in industrial water electrolysis, we have completed a systematic review by constructively discussing the recent progress of Ni-based catalysts for electrocatalytic OER at a large current density, with special focus on the morphology and composition regulation of Ni-based electrocatalysts for achieving extraordinary OER performance. This review will facilitate future research toward rationally designing next-generation OER electrocatalysts that can meet industrial demands, thereby promoting new sustainable solutions for energy shortage and environment issues.

Ir-Doped Bilayer Heterojunction Hollow Nanoboxes for Electrocatalytic Oxygen Evolution.

The fabrication of hollow nanoelectrocatalysts with multilayered heterogeneous interfaces, derived from metal-organic framework (MOF) materials, represents a highly efficient strategy that promotes the oxygen evolution reaction (OER). Within this research, we successfully synthesized a hollow nanobox of Ir-doped ZIF-67@CoFe PBA with bilayer heterointerfaces. The distinctive structure of Ir-ZIF-67@CoFe PBA provides a substantial number of active sites for reaction intermediates, resulting in improved utilization of precious metals. Furthermore, experimental results indicate the outstanding electrocatalytic performance of the optimized Ir-ZIF-67@CoFe PBA, as indicated by a mere 269 mV overpotential at 10 mA·cm-2, accompanied by a small Tafel slope of 80.1 mV·dec-1. Moreover, the Schottky junction formed between the heterojunction and Ir within Ir-ZIF-67@CoFe PBA accelerates the electron-transfer rate, contributing to its exceptional catalytic performance compared to that of a catalyst derived solely from ZIF-67. This distinctive feature of the catalyst holds tremendous application value.

One-pot synthesis of 3D surface-wrinkled PdAu nanospheres for robust alcohols electrocatalysis.

Three dimensional (3D) noble-metal nanomaterials with special surface structures have been regarded as high-performance catalysts for alcohol oxidation on account of their superior thermal stability, electrical conductivity and large specific surface area. Although extensive efforts have been devoted to the preparation of 3D Pd-based catalysts with superior activity and stability, designing a simple, effective and eco-friendly method remains a challenge. Herein, we developed a facile one-step coreduction strategy to synthesize a series of 3D surface-wrinkled PdAu nanospheres (NSs) with tunable Pd/Au atomic ratios and found a universal method to prepare surface-wrinkled PdM (M = Au, Pt, Cu and Pb) NSs. Benefiting from the function of the surfactant cetyltrimethylammonium chloride (CTAC), the synthesized PdAu NSs with different composition possess abundant surface wrinkles, which is beneficial for exposing more electroactive centers. Attributed to the unique geometric morphology and optimized atomic ratio, the PdAu-2 NSs exhibited an optimal mass activity (MA) of 8103 mA mg-1 and 5113 mA mg-1 for the ethylene glycol oxidation reaction (EGOR) and ethanol oxidation reaction (EOR), which was 6.1 and 4.1 times that of commercial Pd/C, respectively. Moreover, the PdAu-2 NSs exhibited superb stability after long-term current-time (i-t) and cyclic voltammetry (CV) tests of the EGOR and EOR. This work not only provides new avenues to engineer PdAu NSs with enhanced electrocatalytic performance but also offers guidance for extending to more 3D PdM (M = other metals) NSs with novel morphology applied to fuel cell fields.

Rapid synthesis of Palladium-Platinum-Nickel ultrathin porous nanosheets with high catalytic performance for alcohol electrooxidation.

Bimetallic two-dimensional (2D) nanomaterials are widely used in electrocatalysis owing to their unique physicochemical properties, while trimetallic 2D materials of porous structures with large surface area are rarely reported. In this paper, a one-pot hydrothermal synthesis of ternary ultra-thin PdPtNi nanosheets is developed. By adjusting the volume ratio of the mixed solvents, PdPtNi with porous nanosheets (PNSs) and ultrathin nanosheets (UNSs) was prepared. The growth mechanism of PNSs was investigated through a series of control experiments. Notably, thanks to the high atom utilization efficiency and fast electron transfer, the PdPtNi PNSs have remarkable activity of methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR). The mass activities of the well-tuned PdPtNi PNSs for MOR and EOR were 6.21 A mg-1 and 5.12 A mg-1, respectively, much higher than those of commercial Pt/C and Pd/C. In addition, after durability test, the PdPtNi PNSs exhibited desirable stability with the highest retained current density. Therefore, this work provides a significant guidance for designing and synthesizing a new 2D material with excellent catalytic performance toward direct fuel cells applications.

Activable Ru-PdRu nanosheets with heterogeneous interface for High-efficiency alcohol oxidation reaction.

Fabricating 2D nanomaterials with heterogeneous structure is a feasible way to improve catalytic performance owing to its large surface area and tunable electron structure. However, such a category has not been widely reported in the field of alcohol oxidation reaction (AOR). In this work, we reported a new type of heterostructure nanosheet with Ru nanoparticles decorated around the edge of PdRu nanosheets (Ru-PdRu HNSs). Particularly, strong electronic interaction and sufficient active sites attributed to the construction of heterogeneous interface, is the key to the superior electrocatalytic behavior of Ru-PdRu HNSs towards methanol oxidation reaction (MOR), ethylene glycol oxidation reaction (EGOR), and glycerol oxidation reaction (GOR). Remarkably, owing to the enhanced electron transfer brought by the introduction of the Ru-PdRu heterogeneous interface, these novel nanosheets are highly durable. Apart from being able to maintain the highest current density after 4000 s chronoamperometry test, Ru-PdRu HNSs can be reactivated with negligible activity loss in MOR and GOR test after four consecutive i-t experiments. Impressively, in the EGOR test, after reactivation, the current density is step-wisely increased, making it one of the best AOR electrocatalysts.

In situ phosphoselenization induced heterointerface engineering endow NiSe2/Ni2P/FeSe2 hollow nanocages with efficient water oxidation electrocatalysis performance.

Exploiting Earth-abundant and highly effective electrocatalysts toward the oxygen evolution reaction (OER) is critical for boosting water splitting efficiency. Herein, we proposed a novel in situ phosphoselenization strategy to fabricate heterostructured NiSe2/Ni2P/FeSe2 (NiFePSe) nanocages with a modified electronic structure and well-defined nanointerfaces. Owing to the strong interfacial coupling and synergistic effect among the three components, the prepared NiFePSe nanocages exhibit superior OER performance with an ultralow overpotential of 242 mV at 10 mA cm-2 and a small Tafel slope of 55.8 mV dec-1 along with robust stability in 1 M KOH. Remarkably, the highly open 3D porous architecture, delicate internal voids, and numerous surface defects endow the NiFePSe nanocages with abundant active sites and enhanced electron mobility. In addition, the super-hydrophilic surface is conducive to facilitating mass transfer between the electrolyte and electrode and rapidly releasing the bubbles. This work may lead to new breakthroughs in the tuning of multi-component transition metal catalysts and the designing of highly active and durable materials for water splitting.

Ce-Modified Flowerlike NiFe-MOF Nanostructure Based on Ion Competitive Coordination for Enhancing the Oxygen Evolution Reaction.

Metal-organic framework (MOF) has become a popular electrocatalyst for the oxygen evolution reaction (OER) because of its large specific surface area and adjustable porosity. Nevertheless, the electrochemical performance of MOFs has been greatly limited by poor intrinsic conductivity and catalytic activity. Herein, we report a Ce-doped nanoflower-like MOF material Ce@NiFe-MOF-5 via a facile ion competitive coordination effect and doping method. Benefiting from the nanoflower structure formed by the stacking of nanosheets, a large number of active sites can be exposed, which favors electron/mass transfer during water oxidation. The coordination substitution of Ce ions not only promoted an increase in the number of active sites on the surface of the nanosheets but also optimized the electronic structure of pristine NiFe-MOF. The well-designed Ce@NiFe-MOF-5 catalysts exhibited superior OER performance under basic conditions, which only required an overpotential of 258 mV at a current density of 10 mA cm-2 and a Tafel slope of 54.44 mV dec-1. Moreover, when Ce@NiFe-MOF-5 served as an anode and Pt/C as a cathode, the two-electrode system only needed 1.56 V to drive overall water splitting at 10 mA cm-2.

Heterostructure engineering and ultralow Pt-loaded multicomponent nanocage for efficient electrocatalytic oxygen evolution.

Developing highly efficient electrocatalysts based on appropriate heterojunction engineering and electronic structure modification for the oxygen evolution reaction (OER) has been extensively recognized as an effective approach to increase the efficiency of water splitting. Herein, ultralow Pt-loaded (1 %) NiCoFeP@NiCoFe-PBA hollow nanocages with well-defined heterointerfaces and modified electronic environment are successfully fabricated. As expected, the obtained Pt-NiCoFeP@NiCoFe-PBA exhibits outstanding performance with a low overpotential of 255 mV at 10 mA cm-2 and a small Tafel slope of 57.2 mV dec-1. More specifically, the highly open three-dimensional structure, exquisite interior voids and abundant surface defects endow Pt-NiCoFeP@NiCoFe-PBA nanocages with more electrochemical active sites. Meanwhile, experimental results and mechanism studies also reveal that the construction of heterogeneous interfaces as well as incorporation of noble metals could readily induce strong synergistic effects and significantly tailor electronic configurations to optimize the binding energy of the intermediates, thereby achieving prominent OER performance.

Photoelectrocatalytic oxidation of ethylene glycol on trimetallic PdAgCu nanospheres enhanced by surface plasmon resonance.

The notable surface plasmon resonance (SPR) effect of some metals has been applied to improve the efficiency of alcohol oxidation reactions, whereas the comprehensive investigation of Cu-assisted photoelectrocatalysis remains challenging. We herein successfully prepared trimetallic PdAgCu nanospheres (NSs) with abundant surface bulges for the advanced ethylene glycol oxidation reaction (EGOR) and compared them with bimetallic PdAg NSs to investigate the performance enhancement mechanism. Impressively, the as-optimized PdAgCu NSs exhibited superb mass activity and electrochemical stability. Moreover, under visible light illumination, the mass activity of PdAgCu NSs increased to 1.62 times compared to that in the dark, and in contrast, the mass activity of PdAg NSs only increased to 1.48 times that in the dark. A mechanistic study indicated that the incorporation of Cu not only strengthens the whole SPR effect of PdAgCu NSs but also further modifies the electronic structure of Pd. This work highlighted that the incorporation of Cu into PdAg NSs further enhanced the photoelectrocatalytic performance and increased noble metal atom utilization, which may provide guidance to fabricate novel and promising nanocatalysts in the field of photoelectrocatalysis.

One-pot synthesis of PdPtAg porous nanospheres with enhanced electrocatalytic activity toward polyalcohol electrooxidation.

Porous nanospheres (PNSs) have great development prospects in the electrocatalysis field because of their structural characteristics, such as a large specific surface area. However, it is still a challenge to find a simple and energy-saving method for the controllable synthesis of PNS nanocatalysts. In this paper, a one-pot CTAC-assisted strategy was developed for the successful formation of PdPtAg PNSs with high porosity at room temperature. Benefitting from the unique structures, optimized composition, acceleration of charge transfer and enhanced resistance to CO poisoning, the PdPtAg PNSs displayed considerably improved electrocatalytic performance with high mass activity and stability toward the ethylene glycol oxidation reaction (EGOR) and glycerol oxidation reaction (GOR). The EGOR and GOR mass activities of PdPtAg were 5.00 A mgmetal-1 and 3.06 A mgmetal-1, which are 6.22 and 1.91 times that of commercial Pd/C, respectively. This work is expected to offer a new path for improving catalytic performance by simple design and adjustment of morphology.

Self-Reconstruction of Fe-Doped Co-Metal-Organic Frameworks Boosted Electrocatalytic Performance for Oxygen Evolution Reaction.

Rational design of facile and low-cost efficient electrocatalysts for oxygen evolution reaction (OER) is crucial to solve the energy crisis. Benefiting from in situ self-reconstruction from metal-organic frameworks (MOFs) to (oxy)hydroxides in alkaline electrolytes, MOFs have become alternative OER catalysts. Thus, Fe-doped Co-MOF nanosheets (Co-MOF/Fe) were prepared and utilized straightforwardly as OER electrocatalysts. CoFe-layered bimetallic hydroxides (CoFe-LDHs) with abundant active sites are obtained from in situ conversion of Co-MOF/Fe after etching by the KOH electrolyte, which are generally actual active species. Meanwhile, the introduction of Fe ions will also produce a synergistic effect that greatly improves the electrocatalytic OER performance. The optimized catalyst (Co-MOF/Fe10) shows exceptional OER activity (η10 = 260 mV) and excellent durability over 50 h. The outstanding OER performance of Co-MOF/Fe10 can also be reflected in the two-electrode hydrolyzer (1.57 V at 10 mA cm-2). This study offers a pathway to probe the catalytic mechanism of MOFs and the rational construction of efficient MOF-derived catalysts.

Green and controllable synthesis of kelp-like carbon nitride nanosheets via an ultrasound-mediated self-assembly strategy.

The application of graphite carbon nitride photocatalysts is hampered by their low specific surface areas, few active sites, and low photogenerated electron-hole transfer rates. Here, we report a green and controllable strategy for synthesizing kelp-like carbon nitride nanosheets through self-assembled materials prepared from melamine and trithiocyanuric acid using sonochemistry. The prepared carbon nitride nanosheets showed superior and long-lasting photocatalytic activity in hydrogen evolution and the degradation of tetracycline hydrochloride. The significantly enhanced photocatalytic performance of carbon nitride nanosheets is attributed to the curled porous nanosheet structure and the appropriate amount of O-doping. This work provides a new design strategy for preparing shape-controlled carbon nitride catalysts via a green, fast, sonochemically mediated self-assembly approach.

Hierarchical Hollow CoWO4-Co(OH)2 Heterostructured Nanoboxes Enabling Efficient Water Oxidation Electrocatalysis.

Rational design and construction of well-defined hollow heterostructured nanomaterials assembled by ultrathin nanosheets overtakes crucial role in developing high-efficiency oxygen evolution reaction (OER) electrocatalysts. Herein, a reliable metal-organic framework-mediated and cation-exchange strategy to tune the geometric structure and multicomponent heterostructures has been proposed for the fabrication of hollow CoWO4-Co(OH)2 hierarchical nanoboxes assembled by rich ultrathin nanosheets. Benefiting from the hierarchical hollow nanostructure, the CoWO4-Co(OH)2 nanoboxes offer plenty of metal active centers available for reaction intermediates. Moreover, the well-defined nanointerfaces between CoWO4 and Co(OH)2 can function as the bridge for boosting the efficient electron transfer from CoWO4 to Co(OH)2. As a consequence, the optimized CoWO4-Co(OH)2 nanoboxes can exhibit outstanding electrocatalytic performance toward OER by delivering 10 mA cm-2 with a low overpotential of 280 mV and a small Tafel slope of 70.6 mV dec-1 as well as outstanding electrochemical stability. More importantly, this CoWO4-Co(OH)2 heterostructured nanocatalyst can couple with Pt/C to drive overall water splitting to achieve 10 mA cm-2 with a voltage of 1.57 V.

Defect and Interface Engineering of Three-Dimensional Open Nanonetcage Electrocatalysts for Advanced Electrocatalytic Oxygen Evolution Reaction.

Defect engineering and interface engineering are two efficient approaches to promote the electrocatalytic performance of transition metal oxides (TMOs) by modulating the local electronic structure and inducing a synergistic effect but usually require costly and complicated processes. Herein, a facile electrochemical etching method is proposed for the controllable tailoring of the defects in a three-dimensional (3D) open nanonetcage CoZnRuOx heterostructure via the in situ electrochemical etching to remove partial ZnO. The highly open 3D nanostructures, numerous defects, and multicomponent heterointerfaces endow the CoZnRuOx nanonetcages with more accessible active sites, moderated local electronic structure, and strong synergistic effect, thereby enabling them to not only deliver an ultralow overpotential (244 mV @ 10 mA cm-2) for oxygen evolution reaction (OER) but also high-performance overall water electrolysis by coupling with commercial Pt/C, with a potential of 1.52 V at 10 mA cm-2. Moreover, experiments and characterizations also reveal that the remaining Zn2+ can facilitate OH- adsorption and charge transfer, which also further improves the electrocatalytic OER performance. This work proposes a promising strategy for creating surface defects in heterostructured TMOs and provides insights to understand the defect- and interface-induced enhancement of OER electrocatalysis.

Hydrogen evolution reaction catalysis on RuM (M = Ni, Co) porous nanorods by cation etching.

The development of efficient and stable nanomaterial electrocatalysts for the hydrogen evolution reaction (HER) is of great significance for renewable energy conversion via water electrolysis. Herein, we have developed a novel class of bimetallic RuM (M = Ni, Co) hollow nanorods (HNRs) through a facile Fe3+ etching strategy, as electrocatalysts for enhancing the HER. Morphological physical characterization and electrochemical tests demonstrated that RuM (M = Ni, Co) HNRs with hollow structures can effectively enhance electrocatalytic activity due to their high specific surface areas. Impressively, the RuNi HNRs exhibited superior HER performance with an overpotential of merely 25.6 mV in 1 M KOH solution at 10 mA cm-2, which is significantly lower than that of commercial Pt/C (44.7 mV). Moreover, the as prepared RuNi HNRs showed excellent stability and could continuously work at a current density of 10 mA cm-2 for 40 h with a negligible increase in potential. The Ru-based HNRs also showed high HER activity in an acidic solution. This study paves a new way for the universal fabrication of bimetallic hollow structured nanomaterials as efficient electrocatalysts for boosting the HER.

Simple Synthesis of PdAg Porous Nanowires as Effective Catalysts for Polyol Oxidation Reaction.

The development of efficient and stable Pd-based electrocatalysts is extremely important to facilitate the development of catalysts for polyol oxidation reactions. To synthesize Pd-based catalysts with excellent catalytic performance, a series of PdAg porous nanowires (PdAg PNWs) with different elemental ratios was constructed by facile synthesis using a seed-mediated method. The synthesized PdAg PNWs have a rough surface and a porous one-dimensional structure, which optimize the specific surface area and surface area of catalysts, thereby providing more active sites for catalysts. PdAg PNWs benefited from the geometric effect of porous nanowires and the synergy between Pd and Ag, showing excellent catalysis (8243.0 and 4137.0 mA mgPd-1) for the ethylene glycol oxidation reaction (EGOR) and glycerol oxidation reaction (GOR). Among them, the optimal Pd62Ag38 PNWs show the highest catalytic activity (6.0 times and 3.9 times higher than Pd/C) and stability compared with Pd57Ag43 PNWs, Pd51Ag49 PNWs, and Pd/C for EGOR and GOR. At the same time, this porous one-dimensional structure also endows PdAg PNWs with faster electron transfer capabilities than Pd/C. This work will likely provide an effective strategy for constructing cost-effective catalysts.

An specific photoelectrochemical sensor based on pillar[5]arenes functionalized gold nanoparticles and bismuth oxybromide nanoflowers for bovine hemoglobin recognition.

In this work, the ultrasensitive photoelectrochemical (PEC) sensor for the detection of bovine hemoglobin (BHb) was developed based on water-soluble pillar[5]arenes (WP5) functionalized gold nanoparticles (Au NPs) and bismuth oxybromide (BiOBr) nanoflowers (Au@WP5/BiOBr). The photoelectrical signal of dopamine (DA) was decreased after adding the different concentrations of BHb due to the formation of hydrogen bond between the COOH groups of BHb molecules and the NH2 group of DA, which could achieve the indirect detection of BHb. Benefiting from the photo-generated electron-holes of BiOBr nanoflowers, the localized surface plasmon resonance (LSPR) effect of Au NPs, the host-guest interaction of WP5 between and DA, the PEC sensor showed a specificallyrecognize toward BHb with a wide detection range of 1.0 × 10-11-1.0 × 10-1 mg/mL and a detection limit of 4.2 × 10-12 mg/mL (S/N = 3). Additionally, the proposed PEC sensor also displayed good stability, remarkable selectivity and provided a promising strategy of design pillar[5]arenes functionalized photoelectric activity nanomaterials for PEC sensing application.

An enhanced photo-electrochemical sensor constructed from pillar [5]arene functionalized Au NPs for ultrasensitive detection of caffeic acid.

Pillar [5]arene, a new water-soluble carboxylatopillar [5]arene ammonium salts (WP5), has been employed as the host for complexation of guest molecules. Herein, a visible light driven WP5 functionalized gold nanoparticles (Au@WP5) was fabricated for ultrasensitive photelectrochemical (PEC) detection of caffeic acid (CA). The ultraviolet-visible spectrum characteristics, PEC response results of samples in caffeic acid solution confirm the localized surface plasmon resonance effect of Au NPs and the host-guest interaction between WP5 and CA are responsible for the enhanced PEC sensing performance. Under optimal conditions, the sensitive PEC sensor constructed with Au@WP5 exhibited the concentration linear range from 0.025 µM to 370 µM and a detection limit of 0.01 µM (S/N = 3). Importantly, the good anti-interference ability, stability and reproducibility of the proposed PEC sensor providing the promising detection application of pillar [5]arene functionalized photoactive materials in food and drinks.