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Atomically precise nanoclusters (NCs) provide opportunities for correlating the structure and electrocatalytic properties at atomic level. Herein, we report the single-atom doping effect and ligand effect on CO2 electroreduction (eCO2RR) by comparing monogold-doped Au1Cu24 and homocopper Cu25 NCs protected by triphenylphosphine or/and tris(4-fluorophenyl)phosphine. Catalytic results revealed that the electronic distribution of Cu25 NCs is enormously contracted by doping Au atoms, entitling it to exhibit the unique inhibition of hydrogen evolution reaction. And the inductive effect of ligand strongly favors the formation of formate in eCO2RR. Overall, this work will provide guidance for the rational design of the copper-based catalysts in the eCO2RR. Tuning the metal core and ligand environment of atomically precise nanoclusters enables the correlation of structural and electrocatalytic properties at an atomic level. Here, single-atom doping and ligand tuning of atomically precise copper clusters is shown to be an effective route to tuning CO2 electroreduction activity and selectivity. [ABSTRACT FROM AUTHOR]

Three-dimensional (3D) Ag/ZnO assemblies with porous nanosheets as building blocks have been designed and selectively prepared via a facial solution method followed by topological morphology conversion with low temperature calcination. The samples were characterized thoroughly by using XRD, SEM, TEM, HRTEM, N 2 isotherms, UV–vis spectroscopy, PL, EIS, Mott-Schottky plots, and photocurrent response. The as-prepared 3D Ag/ZnO architectures were evaluated as photocatalysts for hydrogen evolution and organic pollutants removal from aqueous solution, which demonstrates superior sun-light driven photocatalytic activities to those of ZnO architectures. Nearly 100% photocatalytic degradation of 10 ppm 4-nitrophenol was obtained just for 25 min and 0.4436 mmol g −1 h −1 of hydrogen production rate was achieved over Ag/ZnO architectures. The photocurrent of the Ag/ZnO photoelectrode showed an enhancement of three times of ZnO architectures. The enhanced photocatalytic activity may be attributed to the synergetic effect between 2D ZnO porous single crystalline nanosheets and sliver components, which could not only accelerate separation and migration efficiency of charge carries, but also enhance charge-collection efficiency. [ABSTRACT FROM AUTHOR]

[Display omitted] Multiple surface/interface engineering is an effective approach to develop efficient electrocatalysts for promoting the practical application of electrocatalysis and achieving carbon neutrality. Herein, a deep eutectic liquid precursor containing phosphorus was designed. The self-supported three-dimensional (3D) cobalt-doped Ni 12 P 5 /Ni 3 P nanowire networks coated with a thin layer of carbon (Co-Ni x P@C) were prepared by using an in-situ one-step pyrolysis method. The as-obtained Co-Ni x P@C hybrid possesses a superaerophobic/superhydrophilic surface, which could promote electrolyte diffusion and enhance bubble release. Density functional theory (DFT) calculations reveal that Co-doping in Ni x P@C can promote the adsorption and activation of 5-hydroxymethylfurfural (HMF) molecules, and optimize the energy barrier of H* absorption. The self-supported Co-Ni x P@C was used as an efficient bifunctional electrocatalyst for HMF oxidation coupled with hydrogen evolution reaction (HER) in a 1.0 M KOH solution. A nearly 100 % yield of 2,5-furandicarboxylic acid (FDCA) was achieved. The self-supported Co-Ni x P@C displayed high activity and stability for both HER and HMF conversion. The HMF oxidation coupled with HER can be efficiently driven by a 1.5 V commercial photovoltaic panel under sunlight. This study lays the foundation for large-scale industrialization in sustainable fine-chemical and energy engineering. [ABSTRACT FROM AUTHOR]

[Display omitted] Nanostructured electrocatalysts with unique surfaces and interfaces for hydrogen evolution reaction (HER) are crucial for achieving high performance in universal pH water and natural seawater. Herein, a supramolecular liquid precursor was designed and applied to grow Ni x Co 4-x N/N-doped carbon (NC) ultrathin nanosheet arrays (Ni x Co 4-x N/NC) on carbon cloth through one-step pyrolysis. According to the X-ray absorption spectra, Ni was successfully alloyed into Co 4 N to form Ni x Co 4-x N/NC, which regulates the intrinsic electronic structure and optimizes the adsorption/desorption energy of the catalyst. The unique structure of Ni x Co 4-x N anchored on NC can increase the electron transport efficiency and protect the catalyst from corrosion in the extreme corrosive electrolytes. As a result, the Ni x Co 4-x N/NC catalyst exhibits excellent electrocatalytic HER activity over a wide pH range requiring only 46, 75, and 55 mV at 10 mA/cm2 in the acidic, neutral, and alkaline electrolytes, respectively. Interestingly, the catalyst also shows outstanding HER performance in the natural seawater. This work provides an alternative option for the rational design of efficient electrocatalysts for universal pH water/seawater splitting. [ABSTRACT FROM AUTHOR]

[Display omitted] Constructing photocatalysts with high activity and anti-photocorrosion is a key to harvesting hydrogen energy from seawater efficiently. Herein, graphene oxide closely coupled high-index facets CdZnS with rich sulfur vacancies (Vs-CZS@GO) has been successfully synthesized via one-pot sulfidation accompanied pyrolysis. DFT calculation confirmed the delicate surface/interface/defect engineering endowed high-index facets Vs-CZS@GO with a lower ΔG H* value and significant charge transfer behavior for efficient H 2 -generation. The synergistic effect of sulfur vacancy, high-index facets, and tightly coupling interface not only enhanced intrinsic active sites and carrier separation efficiencies, but also greatly promoted H 2 evolution rate and stability. Consequently, Vs-CZS@GO displayed a significantly high H 2 -generation rate of 23.2 mmol∙g−1∙h−1 in natural seawater under visible-light irradiation, which is up to 82% of that in pure water. This work provides deeply insight into the synergistic regulation of electronic structure for exposed high-index facets photocatalysts via defect engineering and interface engineering for synergistic boosting visible-light-to-H 2 evolution. [ABSTRACT FROM AUTHOR]

[Display omitted] • Co 4 N/NC@CC self-supported electrode was prepared by one-step pyrolysis solution process. • Deep eutectic solvent ensures Co 4 N to in situ couple tightly with NC. • Co 4 N/NC@CC are efficient for biomass conversion and hydrogen fuel production synchronously. • This work contributes to the green production and efficient conversion of renewable energy in industry. Metal nitrides are considered promising catalysts for the hydrogen evolution reaction integrated with electrooxidation reaction of biomass due to their metal-like properties. However, the synthesis of metal nitrides involves multi-step reactions and requires continuous reactions under a large amount of NH 3 atmosphere. Herein, we exploit deep eutectic solvent (DES) to induce in-situ synthesize N -doped carbon (NC) composite Co 4 N ultrathin nanosheets self-supporting electrode on carbon cloth (Co 4 N/NC@CC) without additional input NH 3 atmosphere. XAFS spectra showed that the strong interaction between Co 4 N and NC accelerated the electron transport at the interface, and the ultrathin nanostructure of Co 4 N/NC is beneficial to increasing the catalytic active sites, thereby effectively improving the catalytic performance of Co 4 N/NC@CC. During the HER process, Co 4 N/NC@CC only needs 62, 98, and 60 mV overpotentials to reach a current density of 10 mA/cm2 in alkaline, neutral, and acidic electrolytes. When Co 4 N/NC@CC is used to produce 2,5-furandicarboxylic acid (FDCA) and hydrogen fuel synchronously in alkaline electrolytes, only a low voltage of 1.38 V is required at 10 mA/cm2, and the conversion rate of 5-hydroxymethylfurfural (HMF) is close to 100 % and the selectivity of FDCA is 98.6 %. [ABSTRACT FROM AUTHOR]

The rational design and development of highly efficient non-precious metal chalcogenide electro-catalysts is key but challenging technology for biomass conversion into high-valued chemicals coupling hydrogen evolution. Herein, the NiS quantum dots (QDs) with good dispersibility embedding into wrinkled N,O,S-tri-doped carbon porous nanosheets (NiS@NOSC) implanted in-situ on carbon cloth were synthesized via a facile one-step pyrolysis method. The as-obtained NiS@NOSC porous nanosheets network displays excellent superhydrophilic/superaerophobic surface, facilitating fast diffusion of ion and release of H 2 bubble. The self-supported NiS@NOSC on carbon cloth could serve as both cathode and anode electrodes for high-efficient electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) into high-valued 2,5-furandicarboxylic acid (FDCA) coupling hydrogen evolution requiring only a low potential of 1.51 V to afford 50 mA cm−2. The high electrocatalysis performance is attributed to the synergistic effect of high activity of monodisperse NiS QDs, superhydrophilic/superaerophobic network structure, and the electronic regulation between NOSC and NiS QDs in NiS@NOSC, which has promising foreground to fulfil large-scale commercialize application. [Display omitted] • NiS QDs embedded in N,O,S-tri-doped ultra-thin carbon network were fabricated. • NiS@NOSC exhibited admirable catalytic ability for both HER and HMF oxidation. • The superhydrophilic/superaerophobic nature enable the catalyst with superior performance. • The two-electrode device based on NiS@NOSC || NiS@NOSC only needs 1.51 V to offer 50 mA cm−2. [ABSTRACT FROM AUTHOR]

[Display omitted] • New thermodynamically favorable HER route can be realized on protonated g-C 3 N 4. • S-scheme protonated g-C 3 N 4 QDs/V O -ZnO hybrid was prepared as efficient photocatalyst. • S-scheme fabrication promotes V O generation in ZnO and protonation of g-C 3 N 4 QDs. • V O at hybrid interface significantly facilitates S-scheme electron transfer. • Protonated edge N atom was the main active sites in low energy barrier HER process. Traditional photocatalytic hydrogen evolution path with high energy barrier of proton adsorption limits the reaction efficiency. Specific regulation on active site to realize low energy barrier hydrogen generation provides a new perspective. In this work, an innovative low barrier route is provided on protonated N of g-C 3 N 4 of S-scheme protonated g-C 3 N 4 quantum dots/ZnO hybrid rich in oxygen vacancies (p-CNQDs/V O -ZnO). V O generated by quantum dots doping optimizes the electron structure of S-scheme, whereas the intensive electron directional transmission in S-scheme promotes protonation of p-CNQDs. Profited from the synergies of thermodynamic and dynamic, protons and electrons concentrate at edge-active N accomplish the efficient photocatalytic HER with a 117-fold elevated H 2 evolution. This work provides more possibilities for designing low energy pathway and efficient catalyst in H 2 evolution reaction. [ABSTRACT FROM AUTHOR]

• One-step synthesis of N-doped carbon quantum dots hybridized NiFe-LDH of 1.4 nm thickness. • The BET surface area of the products was 226.7 m2 g−1. • The overpotential is 363 mV at large current density of 500 mA cm−2. • NCD@NiFe-LDH shows excellent durability and stability at 1000 mA cm−2. Herein, we have developed a one-step ionothermal accompanied thermolysis strategy based on metal chloride deep eutectic solvent (DES) precursors to synthesize NiFe layered double-hydroxide ultrathin nanosheets hybridized with N-doped carbon quantum dots (NCD@NiFe-LDH). The NCD@NiFe-LDH hybrid shows hierarchical three-dimensional flower-like morphology assembled with ~1.4 nm ultrathin nanosheets possessing higher surface area values and well conductivity. The as-synthesized NCD@NiFe-LDH hybrid exhibits excellent performance for oxygen evolution reaction (OER) and just require 363 mV to achieve a higher current density of 500 mA cm−2 compared to the state-of-the-art IrO 2 in 0.1M KOH. Besides, NCD@NiFe-LDH hybrid shows long-term stability and satisfactory durability even at 1000 mA cm−2. Such an excellent OER performance at high current density can be ascribed to the unique porous ultrathin structure with abundant active edges and sites and the synergistic effect of the NCD and NiFe-LDH. The work offers a new way for the design and synthesis of other carbon-hybridized LDH ultrathin nanosheets with unique electrochemical properties. [ABSTRACT FROM AUTHOR]

• Graphene oxide encapsulating NiS 2 electrocatalyst was fabricated by a scalable and facile method. • The liquid precursor benefits surface/interface engineering and formation of tightly coupled interface. • The catalyst exhibits highly enhanced HER and OER catalytic activity and durability. • Excellent performance contributes to its unique architecture and coupled interface. Exploring novel tactic to synthesize transition-metal-based electrocatalysts with high activity is crucial to renewable gaseous fuel production. Herein, a simple and efficient synthesis strategy has been successfully developed to in-situ synthesize unique catalysts via embed a graphene oxide (GO) shell membrane in the core of NiS 2 employing an ionic liquid-like NiCl 2 -malonic acid (IL Ni-MA). The elaborately designed IL Ni-MA liquid favors the in-situ growth of breathing GO shell membrane on the surface of NiS 2 along with the formation of gas channel. The moderate breathing GO shell membrane and tightly coupled interface gain the optimum electrocatalysis hydrogen evolution and oxygen evolution performance in 1.0 M KOH. It just demands 57 and 294 mV to achieve a current density of 10 mA cm−2 toward HER and OER, respectively. Moreover, the optimum NiS 2 @GO catalysts can be applied for superior bifunctional catalyst for overall splitting of H 2 O. A cell voltage of 1.52 V and a stable operation for more than 48 h can be gained. The synthetic route may find application in the surface/interfaces engineering of other embedded catalysts toward new energy and environment applications. [ABSTRACT FROM AUTHOR]