State Key Laboratory of Applied Organic Chemistry

The proton exchange membrane (PEM) water electrolysis is one of the most promising hydrogen production techniques. The oxygen evolution reaction (OER) occurring at the anode dominates the overall efficiency. Developing active and robust electrocatalysts for OER in acid is a longstanding challenge for PEM water electrolyzers. Most catalysts show unsatisfied stability under strong acidic and oxidative conditions. Such a stability challenge also leads to difficulties for a better understanding of mechanisms. This review aims to provide the current progress on understanding of OER mechanisms in acid, analyze the promising strategies to enhance both activity and stability, and summarize the state-of-the-art catalysts for OER in acid. First, the prevailing OER mechanisms are reviewed to establish the physicochemical structure-activity relationships for guiding the design of highly efficient OER electrocatalysts in acid with stable performance. The reported approaches to improve the activity, from macroview to microview, are then discussed. To analyze the problem of instability, the key factors affecting catalyst stability are summarized and the surface reconstruction is discussed. Various noble-metal-based OER catalysts and the current progress of non-noble-metal-based catalysts are reviewed. Finally, the challenges and perspectives for the development of active and robust OER catalysts in acid are discussed.

Abstract Photoelectrochemical (PEC) water splitting is a promising method for storing solar energy in the form of hydrogen fuel, but it is greatly hindered by the sluggish kinetics of the oxygen evolution reaction (OER). Herein, a facile solution impregnation method is developed for growing ultrathin (2 nm) highly crystalline β‐FeOOH nanolayers with abundant oxygen vacancies on BiVO 4 photoanodes. These exhibited a remarkable photocurrent density of 4.3 mA cm −2 at 1.23 V (vs. reversible hydrogen electrode (RHE), AM 1.5 G), which is approximately two times higher than that of amorphous FeOOH fabricated by electrodeposition. Systematic studies reveal that the excellent PEC activity should be attributed to their ultrathin crystalline structure and abundant oxygen vacancies, which could effectively facilitate the hole transport/trapping and provide more active sites for water oxidation.

Abstract The asymmetric organocatalysis is definitely one of the most powerful and versatile tools for the rapid construction of various spirocyclic oxindoles. In the past few years, a number of successful strategies based on organocatalysis have been developed for the construction of 3,3′‐spirocyclic oxindoles in high yields and excellent enantioselectivities under mild conditions. In this review, recent advances in this area are summarized and classified according to the spiro ring fused at the 3‐position of the oxindole core.

Abstract The development of highly active and stable oxygen evolution reaction (OER) electrocatalysts is crucial for improving the efficiency of water splitting and metal–air battery devices. Herein, an efficient strategy is demonstrated for making the oxygen vacancies dominated cobalt–nickel sulfide interface porous nanowires (NiS 2 /CoS 2 –O NWs) for boosting OER catalysis through in situ electrochemical reaction of NiS 2 /CoS 2 interface NWs. Because of the abundant oxygen vacancies and interface porous nanowires structure, they can catalyze the OER efficiently with a low overpotential of 235 mV at j = 10 mA cm −2 and remarkable long‐term stability in 1.0 m KOH. The home‐made rechargeable portable Zn–air batteries by using NiS 2 /CoS 2 –O NWs as the air–cathode display a very high open‐circuit voltage of 1.49 V, which can maintain for more than 30 h. Most importantly, a highly efficient self‐driven water splitting device is designed with NiS 2 /CoS 2 –O NWs as both anode and cathode, powered by two‐series‐connected NiS 2 /CoS 2 –O NWs‐based portable Zn–air batteries. The present work opens a new way for designing oxygen vacancies dominated interface nanowires as highly efficient multifunctional electrocatalysts for electrochemical reactions and renewable energy devices.

CoFe₂O₄/graphene oxide hybrids have been successfully fabricated <italic>via</italic> a facile one-pot polyol route, followed by chemical conversion into FeCo/graphene hybrids under H₂/NH₃ atomosphere.

Simultaneous realization of improved activity, enhanced stability, and reduced cost remains a desirable yet challenging goal in the search of electrocatalysis oxygen evolution reaction (OER) in acid. Herein, we report a novel strategy to prepare iridium single-atoms (Ir-SAs) on ultrathin NiCo2O4 porous nanosheets (Ir–NiCo2O4 NSs) by the co-electrodeposition method. The surface-exposed Ir-SAs couplings with oxygen vacancies (VO) exhibit boosting the catalysts OER activity and stability in acid media. They display superior OER performance with an ultralow overpotential of 240 mV at j = 10 mA cm–2 and long-term stability of 70 h in acid media. The TOFs of 1.13 and 6.70 s–1 at an overpotential of 300 and 370 mV also confirm their remarkable performance. Density functional theory (DFT) calculations reveal that the prominent OER performance arises from the surface electronic exchange-and-transfer activities contributed by atomic Ir incorporation on the intrinsic VO existed NiCo2O4 surface. The atomic Ir sites substantially elevate the electronic activity of surface lower coordinated Co sites nearby VO, which facilitate the surface electronic exchange-and-transfer capabilities. With this trend, the preferred H2O activation and stabilized *O have been reached toward competitively lower overpotential. This is a generalized key for optimally boosting OER performance.

The development of highly efficient bifunctional catalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is crucial for improving the efficiency of the Zn–air battery. Herein, we report porous NiO/CoN interface nanowire arrays (PINWs) with both oxygen vacancies and a strongly interconnected nanointerface between NiO and CoN domains for promoting the electrocatalytic performance and stability for OER and ORR. Extended X-ray absorption fine structure spectroscopy, electron spin resonance, and high-resolution transmission electron microscopy investigations demonstrate that the decrease of the coordination number for cobalt, the enhanced oxygen vacancies on the NiO/CoN nanointerface, and strongly coupled nanointerface between NiO and CoN domains are responsible for the good bifunctional electrocatalytic performance of NiO/CoN PINWs. The primary Zn–air batteries, using NiO/CoN PINWs as an air–cathode, display an open-circuit potential of 1.46 V, a high power density of 79.6 mW cm–2, and an energy density of 945 Wh kg–1. The three-series solid batteries fabricated by NiO/CoN PINWs can support a timer to work for more than 12 h. This work demonstrates the importance of interface coupling and oxygen vacancies in the development of high-performance Zn–air batteries.

Abstract Developing bifunctional efficient electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is in high demand for the development of overall water‐splitting devices. In particular, the electrocatalytic performance can be largely improved by designing positive nanoscale‐heterojunction with well‐tuned interfaces. Herein, a novel top‐down strategy is reported to construct the oxide/sulfide heterostructures (N‐NiMoO 4 /NiS 2 nanowires/nanosheets) as a multisite HER/OER catalyst. Starting with the NiMoO 4 nanowires, nitridation in a controlled manner enables activation of Ni sites in NiMoO 4 and then yields oxide/sulfide heterojunction by directly vulcanizing the highly composition‐segregated N‐NiMoO 4 nanowires. The abundant epitaxial heterogeneous interfaces at atomic‐level facilitate the electron transfer from N‐NiMoO 4 to NiS 2 , which further cooperate synergistically toward both the hydrogen and oxygen generation in alkali solution. Furthermore, with N‐NiMoO 4 /NiS 2 grown carbon fiber cloth as the engineering electrode, the assembled N‐NiMoO 4 /NiS 2 –N‐NiMoO 4 /NiS 2 system can deliver a current density of 10 mA cm −2 with the cell voltage of 1.60 V in the water‐splitting reaction. This current density is 3.39 times higher than that of the Pt–Ir set (2.95 mA cm −2 ). The excellent catalytic performance offered of N‐NiMoO 4 /NiS 2 nanowires/nanosheets presents a great example to demonstrate the significance of interface engineering in the field of electrocatalysis.

We report a facile nitrogenation/exfoliation process to prepare hybrid Ni–C–N nanosheets. These nanosheets are <2 nm thin, chemically stable, and metallically conductive. They serve as a robust catalyst for the hydrogen evolution reaction in 0.5 M H2SO4, or 1.0 M KOH or 1.0 M PBS (pH = 7). For example, they catalyze the hydrogen evolution reaction in 0.5 M H2SO4 at an onset potential of 34.7 mV, an overpotential of 60.9 mV (at j = 10 mA cm–2) and with remarkable long-term stability (∼10% current drop after 70 h testing period). They are promising as a non-Pt catalyst for practical hydrogen evolution reaction.

Abstract Transition‐metal sulfides (TMSs) have emerged as important candidates for oxygen evolution reaction (OER) electrocatalysts. Now a hybrid nanostructure has been decorated with CeO x nanoparticles on the surface of ZIF‐67‐derived hollow CoS through in situ generation. Proper control of the amount of CeO x on the surface of CoS can achieve precise tuning of Co 2+ /Co 3+ ratio, especially for the induced defects, further boosting the OER activity. Meanwhile, the formation of protective CeO x thin layer effectively inhibits the corrosion by losing cobalt ion species from the active surface into the solution. It is thus a rare example of a hybrid hetero‐structural electrocatalyst with CeO x NPs to improve the performance of the hollow TMS nanocage.

Abstract Ionogels offer great potential for diverse electric applications. However, it remains challenging to fabricate high‐performance ionogels with both good mechanical strength and high conductivity. Here, a new kind of transparent ionogel with both good mechanical strength and high conductivity is designed via locking a kind of free ionic liquid (IL), i.e., 1‐ethyl‐3‐methylimidazolium dicyanamide ([EMIm][DCA]), into charged poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid) (PAMPS)‐based double networks. On the one hand, the charged PAMPS double network provides good mechanical strength and excellent recovery property. On the other hand, the free [EMIm][DCA] locked in the charged double network through electrostatic interaction offers ionic conductivity as high as ≈1.7–2.4 S m −1 at 25 °C. It is demonstrated that the designed ionogel can be successfully used for a flexible skin sensor even under harsh conditions. Considering the rationally designed chemical structures of ILs and the diversity of charged polymer networks, it is envisioned that this strategy can be extended to a broad range of polymer systems. Moreover, functional components such as conducting polymers, 0D nanoparticles, 1D nanowires, and 2D nanosheets can be introduced into the polymer systems to fabricate diverse novel ionogels with unique functions. It is believed that this design principle will provide a new opportunity to construct next‐generation multifunctional ionogels.

, constitute an important class of materials with a layered crystal structure. Various types of G6-TMD nanomaterials, such as nanosheets, nanotubes and quantum dot nano-objects and flower-like nanostructures, have been synthesized. High thermodynamic stability under ambient conditions, even in atomically thin form, made nanosheets of these inorganic semiconductors a valuable asset in the existing library of two-dimensional (2D) materials, along with the well-known semimetallic graphene and insulating hexagonal boron nitride. G6-TMDs generally possess an appropriate bandgap (1-2 eV) which is tunable by size and dimensionality and changes from indirect to direct in monolayer nanosheets, intriguing for (opto)electronic, sensing, and solar energy harvesting applications. Moreover, rich intercalation chemistry and abundance of catalytically active edge sites make them promising for fabrication of novel energy storage devices and advanced catalysts. In this review, we provide an overview on all aspects of the basic science, physicochemical properties and characterization techniques as well as all existing production methods and applications of G6-TMD nanomaterials in a comprehensive yet concise treatment. Particular emphasis is placed on establishing a linkage between the features of production methods and the specific needs of rapidly growing applications of G6-TMDs to develop a production-application selection guide. Based on this selection guide, a framework is suggested for future research on how to bridge existing knowledge gaps and improve current production methods towards technological application of G6-TMD nanomaterials.

Radical aryl migration reactions are of particular interest to the chemical community due to their potential application in radical chemistry and organic synthesis. The neophyl rearrangements used as radical clocks for examining the radical-molecular reactions have been known for decades. The combinations of these migrations with other radical reactions have provided a wide range of novel synthetic methodologies that are complementary to nucleophilic rearrangements. This review will give an overview of various types of radical aryl migrations, with an emphasis on their mechanistic studies from a historical point of view, as well as their application in tandem radical reactions.

Highly efficient and non-precious metal electrocatalysts for oxygen evolution reactions (OERs) and oxygen reduction reactions (ORRs) are at the heart of key renewable-energy technologies.

Developing convenient doping to build highly active oxygen evolution reaction (OER) electrocatalysts is a practical process for solving the energy crisis. Herein, a facile and low-cost in situ self-assembly strategy for preparing a Ce-doped NiFe-LDH nanosheets/nanocarbon (denoted as NiFeCe-LDH/CNT, LDH = layered double hydroxide and CNT = carbon nanotube) hierarchical nanocomposite is established for enhanced OER, in which the novel material provides its overall advantageous structural features, including high intrinsic catalytic activity, rich redox properties, high, flexible coordination number of Ce3+, and strongly coupled interface. Further experimental results indicate that doped Ce into NiFe-LDH/CNT nanoarrays brings about the reinforced specific surface area, electrochemical surface area, lattice defects, and the electron transport between the LDH nanolayered structure and the framework of CNTs. The effective synergy prompts the NiFeCe-LDH/CNT nanocomposite to possess superior OER electrocatalytic activity with a low onset potential (227 mV) and Tafel slope (33 mV dec–1), better than the most non-noble metal-based OER electrocatalysts reported. Therefore, the combination of the remarkable catalytic ability and the facile normal temperature synthesis conditions endows the Ce-doped LDH nanocomposite as a promising catalyst to expand the field of lanthanide-doped layered materials for efficient water-splitting electrocatalysis with scale-up potential.

A superparamagnetic graphene oxide–Fe3O4 hybrid composite (GO–Fe3O4) was prepared via a simple and effective chemical method. Amino-functionalized Fe3O4 (NH2-Fe3O4) particles are firmly deposited on the graphene oxide sheets. The graphene oxide sheets could prevent NH2-Fe3O4 particles from agglomeration and enable a good dispersion of these oxide particles. The as-prepared GO–Fe3O4 hybrid composite had a much higher thermal stability than graphene oxide. The amount of NH2-Fe3O4 loaded on GO was estimated to be 23.6 wt% by atomic absorption spectrometry. The specific saturation magnetization (Ms) of the GO–Fe3O4 hybrid composite is 15 emu g−1. The magnetic GO–Fe3O4 composite has been employed as adsorbent for the magnetic separation of dye contaminants from water. The adsorption test of dyes (Methylene Blue (MB) and Neutral Red (NR)) demonstrates that it only takes 30 min for MB and 90 min for NR to attain equilibrium. The adsorption capacities for MB and NR in the concentration range studied are 167.2 and 171.3 mg g−1, respectively. The GO–Fe3O4 hybrid composite can be easily manipulated in magnetic field for desired separation, leading to the removal of dyes from polluted water. These GO–Fe3O4 hybrid composites have great potential applications in removing organic dyes from polluted water.

A two step programmed method is developed to load mono dispersed SnO2 nanoparticles onto single layer graphene sheets. The SnO2-G composite has near mono dispersion of the SnO2 nanocrystals as well as a high SnO2 content of over 60 wt%. These outstanding features are desirable and enable the composite material to be an excellent anode material for Li-ion batteries.

Abstract Hydrogel‐based wearable electronic devices have received increasing attention. However, the construction of underwater strain sensors remains a significant challenge because of the swelling of hydrogels in an aquatic environment. This work presents the fabrication of an anti‐swellable hydrogel composed of polyvinyl alcohol (PVA), a copolymer of [2‐(methacryloyloxy) ethyl]dimethyl‐(3‐sulfopropyl) ammonium hydroxide (SBMA) and 2‐hydroxyethyl methacrylate. Interestingly, facile switch of the SBMA moiety from neutral to positively charged status at a low pH value leads to reduced osmotic pressure of the hydrogel for electrostatic repulsion‐driven elimination of water molecules and anti‐swelling. The resulting anti‐swellable hydrogel exhibits high toughness (518 kJ m −3 ) and compressive modulus (8.12 Mpa), ionic conductivity (up to 4.58 S m −1 ), and anti‐swelling behavior (equilibrium swelling ratio of 9% in water for 30 days). An underwater strain sensor based on this anti‐swellable hydrogel is further developed to monitor the movements of underwater sports. High sensitivity is achieved to identify multidirectional motions, including raising the head, swinging the arm, bending the elbow, knee and finger. Therefore, this study offers a facile strategy to generate hydrogel‐based sensors that can be adopted in an underwater environment as well as expands the potential applications of wearable electronic devices.

A new series of five three-dimensional Ln(III) metal–organic frameworks (MOFs) formulated as [Ln4(μ6-L)2(μ-HCOO)(μ3-OH)3(μ3-O)(DMF)2(H2O)4]n {Ln3+ = Tb3+ (1), Eu3+ (2), Gd3+ (3), Dy3+ (4), and Er3+ (5)} was successfully obtained via a solvothermal reaction between the corresponding lanthanide(III) nitrates and 2-(6-carboxypyridin-3-yl)terephthalic acid (H3L). All of the obtained compounds were fully characterized, and their structures were established by single-crystal X-ray diffraction. All products are isostructural and possess porous 3D networks of the fluorite topological type, which are driven by the cubane-like [Ln4(μ3–OH)3(μ3-O)(μ-HCOO)]6+ blocks and μ6-L3– spacers. Luminescent and sensing properties of 1–5 were investigated in detail, revealing a unique capability of Tb–MOF (1) for sensing acetone and metal(III) cations (Fe3+ or Ce3+) with high efficiency and selectivity. Apart from a facile recyclability after sensing experiments, the obtained Tb–MOF material features a remarkable stability in a diversity of environments such as common solvents, aqueous solutions of metal ions, and solutions with a broad pH range from 4 to 11. In addition, compound 1 represents a very rare example of the versatile Ln–MOF probe capable of sensing Ce3+ or Fe3+ cations or acetone molecules.

Abstract Electrochemical water splitting to produce hydrogen and oxygen, as an important reaction for renewable energy storage, needs highly efficient and stable catalysts. Herein, FeS 2 /CoS 2 interface nanosheets (NSs) as efficient bifunctional electrocatalysts for overall water splitting are reported. The thickness and interface disordered structure with rich defects of FeS 2 /CoS 2 NSs are confirmed by atomic force microscopy and high‐resolution transmission electron microscopy. Furthermore, extended X‐ray absorption fine structure spectroscopy clarifies that FeS 2 /CoS 2 NSs with sulfur vacancies, which can further increase electrocatalytic performance. Benefiting from the interface nanosheets' structure with abundant defects, the FeS 2 /CoS 2 NSs show remarkable hydrogen evolution reaction (HER) performance with a low overpotential of 78.2 mV at 10 mA cm −2 and a superior stability for 80 h in 1.0 m KOH, and an overpotential of 302 mV at 100 mA cm −2 for the oxygen evolution reaction (OER). More importantly, the FeS 2 /CoS 2 NSs display excellent performance for overall water splitting with a voltage of 1.47 V to achieve current density of 10 mA cm −2 and maintain the activity for at least 21 h. The present work highlights the importance of engineering interface nanosheets with rich defects based on transition metal dichalcogenides for boosting the HER and OER performance.