Graphene Supported RuNi Alloy Nanoparticles as Highly Efficient and Durable Catalyst for Hydrolytic Dehydrogenation‐Hydrogenation Reactions

Abstract

Here, reduced graphene oxide (RGO) supported surfactant free, RuNi alloy nanoparticles with particle size < 5 nm were synthesized by chemical coreduction route. The synthesized sample was well characterized by various techniques and showed complete solid solution without any extra phase, where Ru lattice is required for nucleation of metallic Ni. The Ru x Ni 100-x /RGO (x = 100, 75, 50 and 25) nanocomposites (NCs) exhibits remarkable activity in hydrolytic dehydrogenation of NH 3 BH 3 (ammonia borane, AB). Among various Ru x Ni 100-x compositions, Ru 50 Ni 50 NPs showed best performance with maximum H 2 evolution rate 9305.6 mL min À1 g À1 and TOF value 236 min À1 at 30 o C, which is one of the best value reported till date. In addition, present activity retained upto 7 th catalytic cycles, showing high durability which makes it a potential candidate for development of NH 3 BH 3 as a H 2 storage material. Moreover, alloy NCs further explored in tandem reduction of nitro and nitrile compounds in presence of AB as H 2 source which again showed best performance with excellent yield (> 99 %) of amine product with short time period of 4.5-10 min. Additionally, NCs exhibits high chemoselectivity and durability towards such organic transformation reactions. This high catalytic efficiency of RGO supported RuNi NPs could be ascribed to synergistic interaction between Ru/Ni metals, high surface area (small sized NPs and graphene sheets), RGO as a support material which prevent agglomeration of particle.

RuNi Nanoparticles Embedded in N‐Doped Carbon Nanofibers as a Robust Bifunctional Catalyst for Efficient Overall Water Splitting

“…The binding energy shifts of the Ni 2p and Ru 3p are in the opposite direction, which can be ascribed to the charge transfer from less electronegative Ni to more electronegative Ru across their interfaces. [42] The synergistic interaction between Ru and Ni metals in Ru 1 Ni 1 -NCNFs caused by effective electronic transfer can result in a relatively moderate hydrogen-metal binding energy and improve the catalytic performance of HER. In order to investigate the effect of different ratios of RuCl 3 and Ni(NO 3 ) 2 on the valence states of Ru and Ni in RuNi-NCNFs, the electrocatalysts of Ru 2 Ni 1 -NCNFs and Ni 2 Ru 1 -NCNFs are also characterized by XPS measurement.…”

“…Compared with Ni‐NCNFs, Ni 2p peaks in the XPS spectrum of Ru 1 Ni 1 ‐NCNFs shift to a higher binding energy. The binding energy shifts of the Ni 2p and Ru 3p are in the opposite direction, which can be ascribed to the charge transfer from less electronegative Ni to more electronegative Ru across their interfaces . The synergistic interaction between Ru and Ni metals in Ru 1 Ni 1 ‐NCNFs caused by effective electronic transfer can result in a relatively moderate hydrogen‐metal binding energy and improve the catalytic performance of HER.…”

Effects of TiO2 structure and Co addition as a second metal on Ru-based catalysts supported on TiO2 for selective hydrogenation of furfural to FA

“…With increasing Co addition, the XPS peaks of Ru 3 p shifted towards lower binding energies while the Co 2 p peaks shifted to higher binding energy, indicating the charge transfer between Ru and Co. The binding energy shifts of the Co 2 p and Ru 3 p are in the opposite direction, which could result from the charge transfer from less electronegative Co to more electronegative Ru 51 , 52 . Thus, the effective electron transfer between Co and Ru in the RuCo alloy in bimetallic catalysts can give rise to improve the catalytic performance.…”

Selectivity Engineering and Efficacy of the Ru–Ni@RGO Catalyst in Hydrogenation of p-tert-Butylphenol to p-tert-Butylcyclohexanol

“…A crumpled sheetlike shape was observed for GO. The catalyst showed a more broken and wrinkled structure (Figure 7a 35 The Ru(0) 3d 5/2 peak was obtained at 280.1 eV, while the Ru 3d 3/2 peak at 284.24 eV was seen obscured by the strong C 1s signal. 23 Furthermore, Ru(0) 3p 3/2 and 3p 1/2 were observed at 461.…”