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Metallic nickel nanoparticles well dispersed in graphitized carbon matrix (Ni@C) by pyrolysis of metal-organic frameworks and leaching treatment of hydrochloric acid could greatly enhance the photocatalytic activity of g-C 3 N 4 under visible light irradiation. For 2.0 wt% Ni@C/g-C 3 N 4 , the average hydrogen evolution rate is 2.15 mmol h −1 g −1 , which is around 88 times higher than that of pure g-C 3 N 4 , and even better than that of platinum-loaded g-C 3 N 4 . The remarkably improved photocatalytic activities through loading Ni@C can be attributed to the cooperative work of Ni nanoparticles and graphene layers, which facilitate the separation of photo-generated carriers and suppress the recombination of the electron-hole pairs. In addition, the hollow onion-like structure can restrain the formation of Ni-hydrogen bonds which modulates desorption of hydrogen. Our studies may open up a promising strategy to design economical noble-metal-free co-catalysts for efficient solar energy conversion. [ABSTRACT FROM AUTHOR]

The construction of efficient and stable non-noble metal bifunctional electrocatalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) presents a challenge in electrocatalytic water splitting. CoS 2 is a promising electrocatalyst that could replace precious metals. In this work, a series of Co-MOF precursors having average particle sizes ranging from the nanometer to the micron scale (86–1084 nm) were synthesized in an unprecedented attempt; Co/CoS 2 heterojunction embedded in nitrogen doped carbon framework (Co/CoS 2 @NC) was prepared through further carbonization and sulfurization. The samples were characterized and evaluated by X-ray powder diffractometer (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and electrochemical techniques. The results indicate that when the size of Co-MOF is less than 300 nm, the cubic structure framework easily collapses to form the spherical structure during the carbonization process. The catalytic activity of Co@NC is size-dependent; Co/CoS 2 @NC exhibited the best performance among the series, with an overpotential of 188 mV for HER and 349 mV for OER at a current density of 10 mA cm−2. This work provides experimental guidance for the design and synthesis of low-cost, efficient, and robust Co-based electrocatalysts. • With Co-MOF cubic nanoparticles as the precursor, Co/CoS 2 @NC was prepared through carbonization and sulfurization. • Co/CoS 2 @NC exhibited the best performance among the series. • The catalytic activity of Co@NC is size-dependent. • This work provides a guidance for the design and synthesis of low-cost, efficient, and robust Co-based electrocatalysts. [ABSTRACT FROM AUTHOR]

Nano-structuring and metal-support interactions are effective methods to improve the electrocatalytic activity of heterogeneous catalysis. In this study, we synthesized nitrogen-doped porous carbon substrates by using a SiO 2 -protected calcination strategy with ZIF-8 as a precursor. The experimental results revealed the prepared porous nitrogen-doped carbon (PNC) to have high dispersion, large specific surface area, and rich pore structure, allowing high exposure of active sites. The carbon support showed optimum characteristics to deposit precious metals with small particle sizes. X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) showed that the N groups on the PNC substrates served as coordination sites for Ru, allowing the formation of ultrafine nanoclusters. The Ru clusters showed good metal dispersion, exposing more active sites and improving the utilization of the precious metal. At a current density of 10 mA/cm2, Ru/PNC showed a minimum overpotential of 40 mV. This work provided a simple and effective method for the preparation of excellent carbon substrates and the synthesis of metal clusters with small particle sizes. N-doped porous carbon (PNC) was synthesized by a SiO 2 -protected calcination strategy by using ZIF-8 as precursor. Compared with Ru/NC, the HER catalytic performance of Ru/PNC catalysts with Ru clusters has been significantly improved. [Display omitted] • Ru nanoclusters was prepared by the EG microwave-assisted method. • N-doped porous carbon was synthesized by a SiO 2 -protected calcination strategy. • Ru/PNC catalyst showed excellent HER-catalytic performance in acidic media. [ABSTRACT FROM AUTHOR]

• In-situ nitrogen doping was achieved by one-step method, a series of Fe M (M = Pt, Pd, Ru, Rh) alloy electrocatalyst NPs with N-doped carbon coatings (Fe M @CN) was synthesized based on a noble metal doped Fe-MOF. • The optimal FePt@CN electrocatalyst demonstrates high electrocatalytic performance in an acidic electrolyte, with low overpotential, high mass activity, and excellent catalytic stability. • The optimal FeRu@CN electrocatalyst obtains an unexpectedly low overpotential of 18 mV in an alkaline electrolyte, which results in a current density of 10 mA cm−2 that is even better than a commercial Pt/C electrocatalyst with 20 wt% Pt loading. • The systematic study presented herein demonstrates that electrocatalysts suitable for different electrolytes can be found in the same alloy system, provides a universal and simple method for synthesizing transition and noble metal alloy electrocatalyst NPs that provides promising prospects for application in industrial electrolysis systems. The alloy catalyst formed by transition metal and a small amount of noble metal has become the most promising substitute for M-based (M = Pt, Pd, Ru, Rh) catalyst. However, due to the direct exposure of the metal core to the electrolyte, it is vulnerable to corrosion and oxidation, which in turn reduces the catalytic stability and is becoming a major obstacle to sustainable hydrogen production. The present work addresses this issue by developing a one-step immersion-adsorption-pyrolysis strategy for synthesizing FeM alloy nanoparticles with N-doped carbon coatings (FeM@CN) for use as electrocatalysts in the HER. The deliberately designed metal-organic framework material was used as the precursor of catalyst synthesis to achieve the carbon coatings and simultaneously the heteroatom in-situ doping for the alloy nanoparticles. The optimal FePt@CN demonstrates excellent catalytic stability and HER activity in an acidic electrolyte medium. The reactions obtain a small overpotential of 28 mV to achieve current densities of 10 mA cm−2, which are comparable to a high-performance commercial Pt/C electrocatalyst with a much higher Pt loading. The FeRu@CN also demonstrates an outstanding performance with an overpotential of only 18 mV to achieve a current density of 10 mA cm−2 in an alkaline medium. In-situ nitrogen doping was achieved by one-step method, a series of Fe M (M = Pt, Pd, Ru, Rh) alloy electrocatalyst NPs with N-doped carbon coatings (Fe M @CN) was synthesized based on a noble metal doped Fe metal organic framework. The systematic study presented herein demonstrates that electrocatalysts suitable for different electrolytes can be found in the same alloy system. [Display omitted] [ABSTRACT FROM AUTHOR]

Cadmiun sulfide (CdS) is considered as a promising semiconductor photocatalyst for its outstanding light absorbance and photoinduced charge separation, but it suffers from severe photocorrosion, mainly due to the sluggish kinetics of holes transfer. In this work, we introduce the strong local Coulomb attraction, which is demonstrated via the in situ K-edge X-ray absorption near edge (XANES) analysis, to accelerate the migration of holes for long-term photocatalytic activity. As a proof-of-concept sample, the hole-attraction Fe 2 O 3 /CdS nanorods evidence an outstanding stability of at least 6 days without obvious deactivation, and feature with an excellent H 2 evolution rate of 20.7 mmol g −1 h −1 . Moreover, this Coulomb attraction strategy can be leveraged to enhance the photocatalytic performance of Zn 0.5 Cd 0.5 S, indicating the wide application of the strategy. [ABSTRACT FROM AUTHOR]

Metallic Ni3P/Ni can be used as a co-catalyst to replace noble metal Pt for efficient photocatalytic hydrogen evolution, due to its excellent trapping-electron ability. The applications of metallic Ni3P/Ni co-catalyst on CdS, Zn0.5Cd0.5S, TiO2 (Degussa P25) and g-C3N4 are further confirmed, indicating its versatile applicability nature like Pt. [ABSTRACT FROM AUTHOR]

The development of low-Pt catalysts is important for the large-scale application of Pt-based catalysts. Catalytic reactions mainly occur on the surface or interface of a material, and thus the surface properties of the catalyst will strongly affect their catalytic activity; this phenomenon has attracted widespread attention. Here, a series of Pt NPs with different chemical states and particle sizes were obtained by changing the light source wavelength, light time, and other conditions of light deposition synthesis. The Pt-TiO 2 catalyst has excellent potential in both photocatalytic hydrogen evolution (4.5 mmol·g−1·h−1) and electrocatalytic hydrogen evolution (26 mV@10 mA cm−2). We also found that the photocatalytic activity is more sensitive to the chemical state of Pt and that reducing the catalyst size can improve the electrocatalytic activity. This work not only provides a green and effective method to adjust the chemical state of precious metals on metal oxides but also helps to understand the impact of surface states on the catalytic process. A series of Pt NPs with different chemical states and sizes were embedded in TiO 2 (B) via a modified photochemical reduction method. The optimized Pt-TiO 2 (B) bifunctional catalyst exhibited excellent p-HER and e-HER catalytic activity. [Display omitted] • A series of Pt NPs with different chemical states and particle sizes were obtained by a photochemical strategy. • The optimized Pt-TiO 2 catalyst has excellent potential in both p-HER (4.5 mmol g−1 h−1) and e-HER (26 mV@10 mA cm−2). • The p-HER is more sensitive to the chemical state of Pt, and reducing the catalyst size improves the e-HER. • This work provides a new idea to promote catalytic activity by adjusting the catalyst's state and size. [ABSTRACT FROM AUTHOR]

• The carboxyl group with electron-withdrawing effect was grafted on the surface of graphite carbon nitride. • The electron-withdrawing effect can promote the separation and migration of carriers to improve photocatalytic performance. • The performance achieved 52 times enhancement with an apparent quantum yield of 15.7 % at 420 nm. Graphitic carbon nitride (g-C 3 N 4) has recently emerged as a promising candidate for photocatalytic hydrogen evolution, but only showed limited activity owing to its sluggish photogenerated carriers separation and migration. Herein, the carboxyl-functionalized g-C 3 N 4 (O CN) was synthesized by a grafting post-treatment method to alleviate the negative influences from this intrinsic drawback. As a result, the surface carboxyl groups greatly improve charge carrier dynamics to suppress carriers recombination via the driving force originated from its electron-withdrawing effects. The resultant O CN exhibits 52 times higher hydrogen evolution rate than the pristine, and possesses a high apparent quantum yield (AQY) of 15.7 % at 420 ± 15 nm. This work deepens the understanding of the surface group related modifications for photocatalytic materials, further providing a promising approach for rational design of photocatalysts with highly efficient solar energy conversion. [ABSTRACT FROM AUTHOR]