Restructuring multi-phase interfaces from Cu-based metal-organic frameworks for selective electroreduction of CO2 to C2H4.

Multi-phase interfaces are promising for surmounting the energy barriers of electrochemical CO2 reduction involving multiple electron transfer steps, but challenges still remain in constructing interfacial micro-structures and unraveling their dynamic changes and working mechanism. Herein, highly active Ag/Cu/Cu2O heterostructures are in situ electrochemically restructured from Ag-incorporating HKUST-1, a Cu-based metal-organic framework (MOF), and accomplish efficient CO2-to-C2H4 conversion with a high faradaic efficiency (57.2% at -1.3 V vs. RHE) and satisfactory stability in flow cells, performing among the best of recently reported MOFs and their derivatives. The combination of in/ex situ characterizations and theoretical calculations reveals that Ag plays a crucial role in stabilizing Cu(i) and increasing the CO surface coverage, while the active Cu/Cu2O interfaces significantly reduce the energy barrier of C-C coupling toward the boosted ethylene production. This work not only proves MOFs as feasible precursors to derive efficient electrocatalysts on site, but also provides in-depth understanding on the working interfaces at an atomic level.

Highly efficient hydrodesulfurization driven by an in-situ reconstruction of ammonium/amine intercalated MoS2 catalysts.

Hydrodesulfurization (HDS) is a commonly used route for producing clean fuels in modern refinery. Herein, ammonium/amine-intercalated MoS2 catalysts with various content of 1T phase and S vacancies have been successfully synthesized. Along with the increment of 1T phase and S vacancies of MoS2, the initial reaction rate of the HDS of dibenzothiophene (DBT) can be improved from 0.09 to 0.55 µmol·gcat-1·s-1, accounting for a remarkable activity compared to the-state-of-the-art catalysts. In a combinatory study via the activity evaluation and catalysts characterization, we found that the intercalation species of MoS2 played a key role in generating more 1T phase and S vacancies through the 'intercalation-deintercalation' processes, and the hydrogenation and desulfurization of HDS can be significantly promoted by 1T phase and S vacancies on MoS2, respectively. This study provides a practically meaningful guidance for developing more advanced HDS catalysts by the intercalated MoS2-derived materials with an in-depth understanding of structure-function relationships.

Redox regulation of Ni hydroxides with controllable phase composition towards biomass-derived polyol electro-refinery.

Electrocatalytic refinery from biomass-derived glycerol (GLY) to formic acid (FA), one of the most promising candidates for green H2 carriers, has driven widespread attention for its sustainability. Herein, we fabricated a series of monolithic Ni hydroxide-based electrocatalysts by a facile and in situ electrochemical method through the manipulation of local pH near the electrode. The as-synthesized Ni(OH)2@NF-1.0 affords a low working potential of 1.36 VRHE to achieve 100% GLY conversion, 98.5% FA yield, 96.1% faradaic efficiency and ∼0.13 A cm-2 of current density. Its high efficiency on a wide range of polyol substrates further underscores the promise of sustainable electro-refinery. Through a combinatory analysis via H2 temperature-programmed reduction, cyclic voltammetry and in situ Raman spectroscopy, the precise regulation of synthetic potential was discovered to be highly essential to controlling the content, phase composition and redox properties of Ni hydroxides, which significantly determine the catalytic performance. Additionally, the 'adsorption-activation' mode of ortho-di-hydroxyl groups during the C-C bond cleavage of polyols was proposed based on a series of probe reactions. This work illuminates an advanced path for designing non-noble-metal-based catalysts to facilitate electrochemical biomass valorization.

Synergistic enhancement of electrocatalytic nitroarene hydrogenation over Mo2C@MoS2 heteronanorods with dual active-sites.

Electrocatalytic hydrogenation (ECH) enables the sustainable production of chemicals under ambient conditions, in which catalysts catering for the different chemisorption of reactants/intermediates are desired but still challenging. Here, Mo2C@MoS2 heteronanorods with dual active-sites are developed to accomplish efficient nitroarene ECH according to our theoretical prediction that the binding of atomic H and nitro substrates would be synergistically strengthened on Mo2C-MoS2 interfaces. They afford high faradaic efficiency (>85%), yield (>78%) and selectivity (>99%) for the reduction of 4-nitrostyrene (4-NS) to 4-vinylaniline (4-VA) in neutral electrolytes, outperforming not only the single-component counterparts of Mo2C nanorods and MoS2 nanosheets, but also recently reported noble-metals. Accordingly, in situ Raman spectroscopy combined with electrochemical tests clarifies the rapid ECH of 4-NS on Mo2C-MoS2 interfaces due to the facilitated elementary steps, quickly refreshing active sites for continuous electrocatalysis. Mo2C@MoS2 further confirms efficient and selective ECH toward functional anilines with other well-retained reducible groups in wide substrate scope, underscoring the promise of dual-site engineering for exploring catalysts.

Enhancing Low-Potential Electrosynthesis of 2,5-Furandicarboxylic Acid on Monolithic CuO by Constructing Oxygen Vacancies.

Electrosynthesis of 2,5-furandicarboxylic acid (FDCA) from the biomass-derived 5-hydroxymethylfurfural (HMF) is one of the most potential means to produce a bioplastic monomer. Copper oxide (CuO) catalyst shows promising prospects due to its high surface activity, conductivity, and stability, but relatively poor capability of oxygen evolution; however, the weak adsorption of substrates and the lack of facile synthetic strategies largely restrict its practical application. Here, a novel facile in situ method, alternate cycle voltammetry (denoted as c) and potentiostatic electrolysis (denoted as p), was proposed to prepare a monolithic cpc-CuO/Cu-foam electrocatalyst. Along with the increment of CuO and its surficial oxygen vacancies (OV), the FDCA yield, productivity, and Faradaic efficiency can reach up to ∼98.5%, ∼0.2 mmol/cm2, and ∼94.5% under low potential of 1.404 VRHE. Such an efficient electrosynthesis system can be easily scaled up to afford pure FDCA powders. In a combinatory analysis via electron paramagnetic resonance spectroscopy, H2 temperature-programmed reduction, open circuit potential, infrared spectroscopy, zeta potential, electrochemical measurement, and theoretical calculation, we found that the CuO was the active phase and OV generated on CuO surface can dramatically enhance the adsorption of *HMF and *OH (* denotes an active site), accounting for its superior FDCA production. This work offers an excellent paradigm for enhancing biomass valorization on CuO catalysts by constructing surficial defects.

Directional Electrosynthesis of Adipic Acid and Cyclohexanone by Controlling the Active Sites on NiOOH.

Dicarboxylic acids and cyclic ketones, such as adipic acid (AA) and cyclohexanone (CHN), are essential compounds for the chemical industry. Although their production by electrosynthesis using electricity is considered one of the most promising strategies, the application of such processes has been hampered by a lack of efficient catalysts as well as a lack of understanding of the mechanism. Herein, a series of monolithic msig/ea-NiOOH-Ni(OH)2/NF were prepared by means of self-dissolution of metal matrix components, interface growth, and electrochemical activation (denoted as msig/ea). The as-synthesized catalysts have three-dimensional cuboid-like structures formed by interconnecting nanosheets composed of NiOOH. By theoretically guided regulation of the amounts of Ni3+ and oxygen vacancies (OV), a 96.5% yield of CHN from cyclohexanol (CHA) dehydrogenation and a 93.6% yield of AA from CHN oxidation were achieved. A combined experimental and theoretical study demonstrates that CHA dehydrogenation and CHN oxidation were promoted by the formation of Ni3+ and the peroxide species (*OOH) on OV. This work provides a promising approach for directional electrosynthesis of high-purity chemicals with in-depth mechanistic insights.

Activating Commercial Nickel Foam to a Highly Efficient Electrocatalyst for Oxygen Evolution Reaction through a Three-Step Surface Reconstruction.

It is highly desired to directly use commercial nickel foam (CNF) as an electrocatalyst for the oxygen evolution reaction (OER) via simple surface reconstruction. In our research, a simple three-step preactivation process was proposed to reconstruct CNF as an efficient OER catalyst, including calcination, high-voltage treatment, and immersing in electrolyte. The optimal CNF after three-step activation reaches an excellent OER performance of 228 and 267 mV at η10 and η100 in alkaline media and can tolerate long-term tests under a large current density of 500 mA·cm-2. The promotion of each step was explored. The calcination step leads to a reconstructive surficial morphology with an enlarged active surface, providing a prerequisite for the following construction steps. The high-voltage treatment changes the valence of surface Ni species, generating phases with higher catalytic activity, and the immersing process introduces Fe heteroatoms into the surface of CNF, boosting the catalytic performance of CNF through Ni-Fe interactions. This research provides a simple method of making high-performance catalysts with accessible nickel foam, a potential for large-scale application in practical industry, and new thinking for the manipulation of Ni-based catalysts.

Chlorine-mediated electrodeposition of hierarchical and hydrophobic copper electrocatalysts for efficient CO2 electroreduction to ethylene.

Hierarchical Cu dendrites fabricated via Cl-mediated electrodeposition afford high C2H4 efficiency (58% faradaic efficiency at -0.9 V vs. RHE) for CO2 electroreduction thanks to not only the optimal hydrophobicity/aerophilicity, but also the dominant distribution of active (100) and (110) facets.

Promoting Amination of Furfural to Furfurylamine by Metal-Support Interactions on Pd/MoO3-x Catalysts.

The reductive amination of carbonyl compounds is one of the most straightforward protocols to construct C-N bonds, but highly desires active and selective catalysts. Herein, Pd/MoO3-x catalysts are proposed for furfural amination, in which the interactions between Pd nanoparticles and MoO3-x supports can be easily ameliorated by varying the preparation temperature toward efficient catalytic turnover. Thanks to the synergistic cooperation of MoV -rich MoO3-x and highly dispersed Pd, the optimal catalysts afford the high yield of furfurylamine (84 %) at 80 °C. Thereinto, MoV species not only acts as the acidic promoter to facilitate the activation of carbonyl groups, but also interacts with Pd nanoparticles to promote the subsequent hydrogenolysis of Schiff base N-furfurylidenefurfurylamine and its germinal diamine. The good efficiency of Pd/MoO3-x within a broad substrate scope further highlights the key contribution of metal-support interactions to the refinery of biomass feedstocks.

Electronic Structure Engineering of Pt Species over Pt/WO3 toward Highly Efficient Electrocatalytic Hydrogen Evolution.

Pt-based supported materials, a widely used electrocatalyst for hydrogen evolution reaction (HER), often experience unavoidable electron loss, resulting in a mismatching of electronic structure and HER behavior. Here, a Pt/WO3 catalyst consisting of Pt species strongly coupled with defective WO3 polycrystalline nanorods is rationally designed. The electronic structure engineering of Pt sites on WO3 can be systematically regulated, and so that the optimal electron-rich Pt sites on Pt/WO3 -600 present an excellent HER activity with only 8 mV overpotential at 10 mA cm-2 . Particularly, the mass activity reaches 7015 mA mg-1 at the overpotential of 50 mV, up to 26-fold higher than that of the commercial Pt/C. The combination of experimental and theoretical results demonstrates that the O vacancies of WO3 effectively mitigate the tendency of electron transfer from Pt sites to WO3 , so that the d-band center could reach an appropriate level relative to Fermi level, endowing it with a suitable Δ G H ∗ $\Delta {G_{{{\rm{H}}^ * }}}$ . This work identifies the influence of the electronic structure on catalytic activity.

Roughness-Dependent Electro-Reductive Coupling of Nitrobenzenes and Aldehydes on Copper Electrodes.

The electro-reductive coupling of nitro and carbonyl compounds enables a facile, environmentally friendly and energy benign transformation toward value-added nitrones or imines, but the selectivity is still challenging. Here, the surface roughness of Cu electrodes is introduced for the first time as the determinant to switch products from nitrones to imines owing to the controllable reduction of nitroarenes to hydroxylamines or amines on tailored CuI /Cu0 interfaces. The roughness-dependent selectivity, that is the decrease of nitrones and the increase of imines with enhanced roughness, is visible in the electro-reductive coupling of nitrobenzene and furfural. Thus, the high selectivity of nitrone (98 %) and imine (80 %) can be achieved on a surface smooth Cu foil and the one electrochemically roughened in the presence of I- , respectively. Such roughness-dependence of nitrone/imine selectivity on Cu electrodes is further verified in a wide substrate scope, highlighting the promise of surface/interfacial engineering for electrochemical synthesis.

Promoted electrocatalytic hydrogenation of furfural in a bi-phasic system.

The promoted electrocatalytic hydrogenation of biomass-derived furfural to 2-methylfuran is for the first time identified in a water/oil bi-phasic system, in which the oil phase can quickly separate hydrophobic products from the electrode/electrolyte interfaces, resulting in a beneficial equilibrium toward hydrodeoxygenation.

Nickel sulfide-oxide heterostructured electrocatalysts: Bi-functionality for overall water splitting and in-situ reconstruction.

Bi-functional electrocatalysts are desired for both hydrogen and oxygen evolution reactions (HER and OER). Herein, facile O2-plasma activation is introduced to improve the bi-functionality via constructing nickel sulfide-oxide heterostructures. Ni3S2-NiOx supported by nickel foam delivers obviously elevated HER and OER activity in comparison with pristine Ni3S2 and recently reported NiSx-based electrocatalysts, featured by the low overpotentials for HER (104 mV) and OER (241 mV) at ±10 mA cm-2 in 1.0 M KOH, as well as a voltage of 1.52 V for overall water splitting. As revealed by in-situ Raman spectroscopy, on the one hand, Ni(OH)2 generated from Ni3S2 during alkaline HER accelerates water dissociation toward the gradually improved performance; on the other hand, this heterostructure undergoes extensive oxidation during OER, leading to excessive NiOOH covering on Ni3S2 and thereby declining activity. These changes are interpreted by the distinct thermodynamic relationship under specific electrochemical conditions via density functional theory calculations.

A 2H-MoS2/carbon cloth composite for high-performance all-solid-state supercapacitors derived from a molybdenum dithiocarbamate complex.

A molecular complex Mo2O2(µ-S)2(Et2dtc)2 (dtc = dithiocarbamate) is prepared and loaded onto carbon cloth (CC) through facile solvothermal treatment, followed by subsequent single-source pyrolysis. This results in a highly porous 2H-MoS2/CC composite with a sponge-like stacked lamellar morphology. Due to its high porosity and unique nano/microstructure, the MoS2/CC composite exhibits a specific capacitance of 550.0 F g-1 at 1 A g-1, outperforming some 1T-MoS2 based electrodes. The composite is further assembled into a symmetric all-solid-state supercapacitor, which can be operated stably at a wide potential window and shows a specific capacitance of 127.5 F g-1 at 1 A g-1. In addition, the device delivers a high energy density of 70.8 W h kg-1 at 1 kW kg-1, which still remains 15.0 W h kg-1 at 18.0 kW kg-1. 75% of the performance of the device can be retained after 8000 cycles. Such remarkable electrochemical performance is attributed to its novel nano/microstructures with a large surface area, convenient ion transport pathways, enhanced conductivity, and improved structural stability. Thus, this work demonstrates a highly promising dithiocarbamate-based single-precursor pyrolysis route towards the fabrication of metal sulfides/carbon composites for energy storage applications.

Single-layer CoFe hydroxides for efficient electrocatalytic oxygen evolution.

Single-layer CoFe layered double hydroxides (CoFe LDH-S) are successfully fabricated under near-anhydrous conditions due to the weakened hydrogen bonds between monolayers. Benefiting from the single-layer structure with rich defects and disordered lattices, CoFe LDH-S affords superior OER activity compared to its bulky counterparts and most of the recently reported non-precious electrocatalysts.

Interlayer engineering of molybdenum disulfide toward efficient electrocatalytic hydrogenation.

Electrocatalytic hydrogenation (ECH) enables the sustainable production of chemicals under ambient condition; however, suffers from serious competition with hydrogen (H2) evolution and the use of precious metals as electrocatalysts. Herein, molybdenum disulfide is for the first time developed as an efficient and noble-metal-free catalyst for ECH via in situ intercalation of ammonia or alkyl-amine cations. This interlayer engineering regulates phase transition (2H â†’ 1 T), and effectively ameliorates electronic configurations and surface hydrophobicity to promote the ECH of biomass-derived oxygenates, while prohibiting H2 evolution. The optimal one intercalated by dimethylamine (MoS2-DMA) is capable of hydrogenating furfural (FAL) to furfuryl alcohol with high Faradaic efficiency of 86.3%-73.3% and outstanding selectivity of >95.0% at -0.25 to -0.65 V (vs. RHE), outperforming MoS2 and other conventional metals. Such prominent performance stems from the enhanced chemisorption and surface hydrophobicity. The chemisorption of H intermediate and FAL, synchronously strengthened on the edge-sites of MoS2-DMA, accelerates the surface elementary step following Langmuir-Hinshelwood mechanism. Moreover, the improved hydrophobicity benefits FAL affinity to overcome diffusion limitation. Discovering the effective modulation of MoS2 from a typical H2 evolution electrocatalyst to a promising candidate for ECH, this study broadens the scope to exploit catalysts used for electrochemical synthesis.

Core-shell nanostructured electrocatalysts for water splitting.

As the cornerstone of the hydrogen economy, water electrolysis consisting of the hydrogen and oxygen evolution reactions (HER and OER) greatly needs cost-efficient electrocatalysts that can decrease the dynamic overpotential and save on energy consumption. Over past years, observable progress has been made by constructing core-shell structures free from or with few noble-metals. They afford particular merits, e.g., a highly-exposed active surface, modulated electronic configurations, strain effects, interfacial synergy, or reinforced stability, to promote the kinetics and electrocatalytic performance of the HER, OER and overall water splitting. So far, a large variety of inorganics (carbon and transition-metal related components) have been introduced into core-shell electrocatalysts. Herein, representative efforts and progress are summarized with a clear classification of core and shell components, to access comprehensive insights into electrochemical processes that proceed on surfaces or interfaces. Finally, a perspective on the future development of core-shell electrocatalysts is offered. The overall aim is to shed some light on the exploration of emerging materials for energy conversion and storage.

N-doped carbon encapsulated CoMoO4 nanorods as long-cycle life anode for sodium-ion batteries.

Volume expansion and poor conductivity result in poor cyclability and low rate capability, which are the major challenges of transition-metal oxide as anode materials for sodium-ion batteries (SIBs). Herein, N-doped carbon encapsulated CoMoO4 (CoMoO4@NC) nanorods are developed as excellent anode materials for SIBs with long-cycle life. The N-doped carbon shells serve as buffer to accommodate severe volume changes during sodiation/desodiation, and at the same time improve electronic conductivity and activate surface sites of CoMoO4. The optimized composite presents rapid reaction kinetics and excellent cycle stability. Even at a high current density of 1 A g-1, it still shows long-cycle life and maintains specific capacity of 190 mAh g-1 after 3200 cycles. Furthermore, CoMoO4@NC anode is applied to match with Na3V2(PO4)3 cathode to assemble full-cells, in which it accomplishes reversible capacity of 152 mAh g-1 after 100 cycles, with capacity retention of 75% at a current density of 1 A g-1, highlighting the practical application for SIBs.

Revealing Facet Effects of Palladium Nanocrystals on Electrochemical Biosensing.

Noble-metal nanocrystals (NCs) are functional segments of biosensing platforms, but their sensitivity and facet effects are still challenging. Conventional synthesis using surfactants to direct crystal growth unfortunately causes adsorbate-surface hindrance, which not only reduces sensing responses but also leads to misunderstanding on facet-dependence. Herein, we utilize electrochemical CO displacement to remove residual surfactants from facet-engineered Pd NCs, and further investigate the structure-activity relationship on specific facets, for example, {100} in cubes, {111} in octahedrons, and {110} in rhombic dodecahedrons. Along with the remarkably boosted response, facet dependence is obvious for H2O2 sensing after surface cleaning. The Pd{100} shows high sensitivity, low detection limit, and wide applicable concentration range, superior to the {110} and {111}. This can be theoretically interpreted by the befitting *OH binding on {100} and thereby the facilitated H2O2 reduction kinetics. The outstanding selectivity to H2O2 ensures the high efficiency of Pd NCs to measure intracellular H2O2 and recognize different types of cancer cells. Moreover, facet effects are also evidenced in glucose detection, highlighting that this work can provide guidelines to design efficient sensing platforms.

Efficient electrochemical biosensing of hydrogen peroxide on bimetallic Mo1-xWxS2 nanoflowers.

Two-dimensional transition-metal dichalcogenides can serve as emerging biosensing platforms after rational structural optimization. Herein, we develop a series of Mo1-xWxS2 and investigate the composition-dependent sensing of hydrogen peroxide (H2O2). Among them, the Mo0.75W0.25S2 affords high sensitivity (1290 µA mM-1 cm-2), good selectivity, and wide applicable concentration range (4 × 10-1-1.0 × 104 µM). As indicated by theoretical investigations, such prominent performance stems from the bimetallic electronic configurations and the enhanced *OH binding on surface. Moreover, the Mo0.75W0.25S2 is capable of monitoring trace amounts of H2O2 released from normal cells and various cancer cells, which provides efficient cell detection for clinical diagnosis. In addition, the composition-dependence, as a result of electronic modulation on Mo1-xWxS2 surface, is further evidenced on electrocatalytic hydrogen evolution reaction, which highlights the promise in sensing and electrocatalysis that share similar electrochemical fundamentals.