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[Display omitted] Construction of semiconductor heterojunctions which promote the separation and transport of photogenerated carriers is an effective strategy for improving photocatalytic reaction efficiency. Based on the anisotropic electrical conductivity of layered ZnIn 2 S 4 (ZIS) photocatalyst, an efficient heterojunction should be constructed along the layer plane of ZIS, that is, a J type heterojunction. However, achieving controllable synthesis of the oriented heterojunction of ZIS faces challenges. Herein, we develop a facile, cost-effective and spatially-selective cation exchange synthesis approach to construct J type ZnIn 2 S 4 @CdIn 2 S 4 (J-ZIS@CIS) heterojunction using a flower-like hexagonal ZIS as the parent material. The developed synthesis approach can also control crystal structure of the heterojunction component CIS. This work presents a facile and controllable synthesis strategy to construct oriented anisotropic heterojunctions that are otherwise inaccessible. The as-prepared J-ZIS@CIS heterojunction displays a greatly enhanced photocatalytic hydrogen evolution activity with a rate of 183 μmol h−1, 2.77 times higher than that of pristine ZIS. Furthermore, the possible photocatalytic reaction mechanism is presented for the heterojunction. [ABSTRACT FROM AUTHOR]

[Display omitted] • A volume OER (VOER) strategy for layered hydroxides was presented. • Phosphate-intercalated Ni(OH) 2 /NiOOH loaded on Ni foam was prepared as a VOER catalyst. • The catalyst displays better OER activity than benchmark RuO 2 and most Ni-based catalysts. • The long-term stability is over 1000 h, much better than other Ni-based OER catalysts. • The role of phosphate intercalation on VOER has been revealed. Layered Ni(OH) 2 /NiOOH hydroxides are effective oxygen evolution reaction (OER) electrocatalysts, but their activities are still inferior to those of benchmark RuO 2 and IrO 2. Notably, the long-term stability becomes a significant challenge. Herein, we present a novel volume OER (VOER) strategy to solve the problems via pre-intercalation of phosphate. Phosphate-intercalated Ni-Ni(OH) 2 /NiOOH electrode was prepared by a two-step electrochemical method. The obtained porous electrode exhibits outstanding OER performance in the alkaline phosphate electrolyte with the overpotentials of 129 and 243 mV at 10 and 100 mA cm−2, respectively, and stability for 1000 h. The exceptional performance is mainly ascribed to effective VOER and elimination of the interlayer-produced protons, because the phosphate-intercalation enhances the interlayer water content, interlayer spacing and proton transport ability, endows the interlayers with proton buffering capacity, and alters the chemical environment of the interlayer Ni-O. The finding provides a strategy to develop highly efficient and stable OER materials and reaction systems for layered transition metal hydroxides. [ABSTRACT FROM AUTHOR]

It is highly desirable to develop efficient and cost-effective composite catalysts to replace noble metal Pt for hydrogen evolution reaction (HER). For an excellent HER catalyst, both the adsorption and desorption of intermediate H atoms on it should be easy. However, except metal platinum, most individual species cannot satisfy this requirement. Fe-B is an active HER catalyst with strong ability to adsorb H atoms. In our previous work, we found that when Fe-B alloy was decorated with metal Fe particles (Fe-B@Fe), the resultant composite displayed a significant synergic effect for HER compared to single Fe-B and Fe. The role of the decorated Fe on Fe-B is to improve H 2 desorption. Because the desorption of H 2 molecule from Ni is easier than from Fe, we expect Fe-B@Ni to be a more efficient HER catalyst than Fe-B@Fe. Herein, we transform Fe-B@Fe into Fe-B@Ni by a facile displacement reaction. As a proof of concept, the as-prepared Fe-B@Ni catalyst exhibits much higher electrocatalytic and photocatalytic activity for hydrogen production than the pristine Fe-B@Fe. At the current density of −100 mA cm−2, the overpotential of Fe-B@Ni in 1.0 mol L−1 KOH is close to that of 20 wt% Pt/C. The highest apparent quantum yield (AQY) for dye-sensitized photocatalytic hydrogen evolution reaches 51% at 420 nm. The possible mechanisms have been proposed. These findings provide new insights for designing and fabricating new HER composite catalysts for electrocatalytic and photocatalytic hydrogen evolution. [ABSTRACT FROM AUTHOR]