The catalytic dehydrogenation of hydrazine borane (N2H4BH3) and hydrous hydrazine (N2H4·H2O) for H2 evolution is considered as two of the pivotal reactions for the implementation of the hydrogen-based economy. A reduction rate controlled strategy is successfully applied for the encapsulating of uniform tiny NiPt alloy nanoclusters within the opening porous channels of MOFs in this work. The resultant Ni0.9Pt0.1/MOF core–shell composite with a low Pt content exerted exceedingly high activity and durability for complete H2 evolution (100% hydrogen selectivity) from alkaline N2H4BH3 and N2H4·H2O solution. The features of small NiPt alloy NPs, strong synergistic effect between NiPt alloy NPs and the MOF, and open pore structure for freely mass transfer made NiPt/MIL-101 an excellent catalyst for highly efficient H2 evolution from N2H4BH3 or N2H4·H2O.

The structural stability, electronic and catalytic properties of Aun (n = 1–4) nanoclusters supported on monolayer MoS2 have been investigated based on first principle DFT calculation with van der Waals (vdW) corrections. Our results show that all Aun (n = 1–4) nanoclusters prefer to bind vertically on the top S sites of the monolayer MoS2. And the relative stability of Aun (n = 1–4) clusters in gas phase is not preserved after landing on monolayer MoS2. By including van der Waals (vdW) corrections with different approaches, we found that the van der Waals correction increased the adsorption energies for all supported Aun (n = 1–4) clusters with the order of Eads(PBE-D2) > Eads(PBE-D3) > Eads(optB86b-vdW) > Eads(PBE). And the van der Waals effects can also change the order of stability and the energy differences of various deposition configurations. In addition, the binding of O2 is also modeled, showing significantly enhanced adsorption properties and catalytic activation toward O2 adsorption, especially for that on supported Au1 and Au3 clusters with magnetic properties, with respect to that on supported Au2 and Au4 clusters with nonmagnetic properties. The current study provides further insight into the adsorption and catalytic properties of small gold clusters supported on monolayer MoS2, which play a crucial role in the activation of O2.

•NiM (M = Cr, Mo, W) NPs were facilely prepared via a surfactant-aided co-reduction method.•NiM NPs show a higher catalytic activity than pure Ni NPs for hydrolysis of NH3BH3.•Ni0.9Cr0.1, Ni0.9Mo0.1, and Ni0.8W0.2 NPs show the highest activities among the Ni1-xMx NPs.•The optimized NiM NPs can also perform efficiently in hydrolysis of N2H4BH3.In this work, a series of Ni1-xMx (M = Cr, Mo, W) nanoparticles (NPs) have been successfully synthesized via a simple surfactant-aided co-reduction method and employed as highly efficient and cost effective catalysts for hydrogen generation from aqueous solution of ammonia borane (NH3BH3, AB) at room temperature. It is found that the as-synthesized NiM NPs (M = Cr, Mo, W) exhibit much higher catalytic performance for the hydrolysis of AB as compared to that of pure Ni NPs. In addition, among all the Ni1-xMx (M = Cr, Mo, W) NPs, the Ni0.9Cr0.1, Ni0.9Mo0.1, and Ni0.8W0.2 NPs show the highest catalytic activities with the turnover frequency (TOF) values of 10.7, 27.3 and 25.0 mol H2 (mol metal min)−1, respectively. Remarkably, these optimized NiM catalysts can also perform efficiently in the hydrolysis of hydrazine borane (N2H4BH3, HB). The present low-cost and high-performance of the NiM catalysts system may encourage the practical application of AB and HB as the promising chemical hydrogen storage materials.Download high-res image (134KB)Download full-size imageNoble-metal-free NiM (M = Cr, Mo, W) NPs have been facilely synthesized via a simple surfactant-aided co-reduction method, which showed a higher catalytic activity than that of pure Ni for the hydrolysis of ammonia borane and hydrazine borane at room temperature.

Ni nanoparticles modified with a Mo dopant have been synthesized on graphene sheets via a facile chemical reduction route, which show the highest catalytic activity reported to date for noble-metal-free catalysts for hydrogen evolution from the hydrolysis of ammonia borane with a turnover frequency value as high as 66.7 mol H2 (mol metal min)−1.

Ag–CeO2 nanocomposites (Ag@CeO2 NCs) with a core–shell structure have been successfully synthesized through the combination of a redox reaction and the reverse micelle technique without any additional reductants or surfactants. Under a N2 atmosphere, the redox reaction automatically occurs between Ag+ and Ce3+ in an alkaline solution, resulting in the formation of Ag@CeO2 NCs by the self-assembly process. By using the XRD, FE-SEM, TEM, XPS, and ICP methods, the characterized results of Ag@CeO2 NCs show that Ag nanoparticles (NPs) with a diameter of 3–7 nm are surrounded by CeO2 NPs. Compared to CeO2 supported Ag NPs, free Ag NPs, and CeO2, the as-synthesized Ag@CeO2 NCs exhibit a superior catalytic activity and high sustainability for the hydrogenation of 4-nitrophenol (C6H5NO3, 4-NP) and 2-nitroaniline (C6H6N2O2, 2-NA) with sodium borohydride (NaBH4) in water solution at room temperature. The Ag@CeO2 NCs can achieve a complete reduction of 4-NP and 2-NA with turnover frequencies (TOF) of 138.7 and 109.8 h−1, respectively. The durability tests show that the Ag@CeO2 NCs are still highly active for the reduction of 4-NP and 2-NA, preserving 98% and 95% of their initial catalytic activity even after ten runs.

•Rh–Ni/Ce(OH)CO3 were synthesized by a facile co-reduction method.•Rh55Ni45/Ce(OH)CO3 showed high activity and H2 selectivity for decomposition of hydrazine.•A high TOF value of 150 h−1 at 30 °C was obtained.•Activation energy of Rh55Ni45/Ce(OH)CO3 was measured to be 38.8 kJ/mol.Bimetallic Rh–Ni nanoparticles (NPs) immobilized on the cerium hydroxide carbonate (Ce(OH)CO3) have been successfully prepared by a facile co-reduction route, and characterized by XRD, SEM, TEM, EDX, ICP, XPS, and TG-DTA. The as-synthesized Rh–Ni/Ce(OH)CO3 nanocomposites (NCs) with different metal compositions were applied as the highly efficient catalysts for hydrogen generation from the alkaline solution of hydrazine (N2H4). Especially, the Rh55Ni45/Ce(OH)CO3 NCs exerted the highly activity and 100% H2 selectivity for the decomposition of hydrazine, providing high turnover frequency (TOF) values of 150 h−1 at 30 °C and 395 h−1 at 50 °C, respectively, relative high values for the metal catalysts. The activation energy for the decomposition of hydrazine catalyzed by Rh55Ni45/Ce(OH)CO3 NCs was measured to be 38.8 kJ/mol, lower than most of the values reported for this reaction using many different catalysts. This excellent catalytic performance could be attributed to not only the strain and ligand effects between Rh and Ni, but also the strong interaction between RhNi NPs and Ce(OH)CO3 support. Such a highly catalyst may greatly encourage the practical application of hydrazine as a hydrogen storage material.A facile and effective approach for one step co-reduction route fabrication of Rh55Ni45/Ce(OH)CO3 nanocomposites, which exhibited excellent catalytic activity for hydrogen generation from the decomposition of N2H4 at 30 °C.

CeOx-modified RhNi nanoparticles (NPs) grown on reduced graphene oxide (rGO) (RhNi@CeOx/rGO) have been facilely prepared and successfully used as highly efficient catalysts for the rapid and complete hydrogen generation from aqueous solution of hydrazine borane (N2H4BH3) and hydrazine (N2H4), respectively. It was found that the CeOx-doped RhNi NPs with a size of around 3.5 nm were highly dispersed on rGO nanosheets. Among all the catalysts investigated, the optimized catalyst Rh0.8Ni0.2@CeOx/rGO with a CeOx content of 13.9 mol% exhibited the highest catalytic performance. The total turnover frequency (TOF) of Rh0.8Ni0.2@CeOx/rGO for hydrogen generation from N2H4BH3 reached 666.7 h−1 (molH2 mol(Rh+Ni)−1 h−1) at 323 K, which was among the highest of all the catalysts reported to date for this reaction, 10-fold higher than that of the benchmark catalyst Rh0.8Ni0.2, and 3-fold higher than that of Rh0.8Ni0.2 with a CeOx dopant (Rh0.8Ni0.2@CeOx) and a rGO support (Rh0.8Ni0.2/rGO). Even at room temperature, Rh0.8Ni0.2@CeOx/rGO can achieve a complete hydrogen generation from N2H4BH3 and N2H4 with a TOF value of 111.2 and 36.4 h−1. This excellent catalytic performance might be attributed to the synergistic structural and electronic effects of the RhNi NPs, CeOx dopant, and rGO support. Moreover, this general method can be easily extended to facile synthesis of other metal/rGO systems with the doping of rare-earth oxides for more applications.

•Ni1−xPtx–CeO2 nanocomposites were easily synthesized.•The as-synthesized Ni0.9Pt0.1–CeO2 sample is in amorphous state.•Ni0.9Pt0.1–CeO2 exhibit high activity for dehydrogenation of hydrazine borane.•The TOF value 234 h−1 is much higher than most of the catalysts reported.NiPt–CeO2 nanocomposites (NCs) have been easily prepared via a surfactant aided co-reduction route and characterized by ICP-AES, XRD, TEM, HRTEM, SAED, EDX and XPS techniques. The characterized results show that the NiPt–CeO2 NCs with an average particle size of 3 nm are in amorphous state and well-dispersed. The as-synthesized NiPt–CeO2 NCs are successfully applied as a highly efficient catalyst for rapid and high-extent dehydrogenation of hydrazine borane (Hy-B). The amorphous NiPt–CeO2 NCs obtained due to the addition of CeO2 display much better activity than that of Ni-, Pt–CeO2, and crystalline NiPt NCs. Especially, Ni0.9Pt0.1–CeO2 NCs with a low noble-metal content exhibit markedly high catalytic activity to release 5.74 equiv. (H2 + N2) per Hy-B in only 12.3 min with a high turnover frequency (TOF) value of 234 h−1 (molH2·molmetal−1·h−1). In the presence of this special amorphous state Ni0.9Pt0.1–CeO2 nanocatalyst, the hydrolysis of the group BH3 and the decomposition of the moiety N2H4 occur simultaneously and thus accelerate the rate of releasing hydrogen from Hy-B. This excellent catalytic performance is due to the synergistic effect between NiPt and CeO2 and the promotion effect of NaOH.

Ultrafine Ni–Pt alloy NPs grown on graphene (NiPt/graphene) have been facilely prepared via a simple one-step coreduction synthetic route and characterized by transmission electron microscopy, energy-dispresive X-ray spectroscopy, X-ray diffraction, inductively coupled plasma atomic emission spectroscopy, X-ray photoelectron spectroscopy, Raman and Fourier transform infrared methods. The characterized results showed that ultrafine Ni–Pt NPs with a small size of around 2.3 nm were monodispersed on the graphene nanosheet. Compared to the pure Ni0.9Pt0.1 alloy NPs, graphene supported Ni0.9Pt0.1 alloy NPs exhibited much higher activity and hydrogen selectivity (100%) toward conversion of hydrazine borane (HB) to hydrogen. It is first found that the durability of the catalyst can be greatly enhanced by the addition of an excess amount of NaOH in this reaction, because of the neutralization of NaOH by the byproduct H3BO3 produced from the hydrolysis of HB. After six cycles of the catalytic reaction, no appreciable decrease in activity was observed, indicating that the Ni0.9Pt0.1/graphene catalysts have good durability/stability.Keywords: Decompose; Durability; H2; H3BO3; Hydrolysis; N2H4BH3; NaOH; Neutralization;

Diverse mesoporous CuO nanostructures have been prepared by a facile and scaleable wet-chemical method and reduced to mesoporous Cu nanostructures by using the reductant ammonia borane (AB). These mesoporous Cu nanostructures have been applied as a catalyst for hydrogen generation from the methanolysis of AB. The catalytic results show that the reaction rate and the amount of hydrogen evolution significantly relied on their morphologies. Compared with the nanosheet-like, bundle-like and dandelion-like Cu, the flower-like Cu nanostructures exhibit the highest catalytic activity with a total turnover frequency (TOF) value of 2.41 mol H2 mol catalyst−1 min−1 and a low activation energy value of 34.2 ± 1.2 kJ mol−1 at room temperature. Furthermore, the flower-like Cu nanostructures have also shown excellent activity in recycling tests. The low cost and high performance of Cu nanocatalysts may offer high potential for its practical application in hydrogen generation from the methanolysis of AB.

Ag–SiO2 nanocomposites (NCs) with “plum-pudding” structure have been synthesized using a facile reverse micelle method. The as-synthesized Ag–SiO2 NCs were calcined at 623 K to remove the surfactants and then characterized by XRD, FE-SEM, TEM, EDX, ICP and N2 adsorption–desorption. The obtained results demonstrated that many ultrafine Ag nanoparticles (NPs) with size of ~2 nm are well dispersed in each SiO2 nanosphere (28 nm). In comparison with free Ag NPs and SiO2 supported Ag NPs, the Ag–SiO2 NCs exhibited a better catalytic activity for the reduction of 4-nitrophenol with a turnover frequency of 489 h−1 at room temperature. Ag–SiO2 NCs also displayed a superior catalytic activity for hydrogenation of 2-NP and 3-NP. The activation energy of Ag–SiO2 NCs was estimated to be about 34.4 kJ mol−1, which was lower than most of the reported values for the same reaction using Ag-based catalysts, indicating the superior catalytic performance of these plum-pudding structured catalysts.

•Ag/SiO2–CoFe2O4 NCs are in situ synthesized and used as catalyst for hydrolysis of AB.•Ag/SiO2–CoFe2O4 exhibit superior catalytic activity than single Ag or SiO2–CoFe2O4.•The measured TOF value 264 mol H2 (mol Ag min)−1 is among the highest of all the reported Ag-based catalysts.•These catalysts can be readily separated by an external magnet and show good recycle stability.In this paper, we reported a facile and effective approach for fabrication of SiO2–CoFe2O4 supported dispersed Ag nanoparticles (NPs). The as-synthesized nanocomposites (NCs) were characterized by XRD, TEM, EDX, ICP, XPS and N2 adsorption-desorption, and used as catalyst for H2 production from hydrolysis of ammonia borane (AB). A poorly active catalyst of Ag NPs was dramatically converted into a highly active catalyst, in the presence of inactive SiO2–CoFe2O4 support. Among all the Ag(0)/SiO2–CoFe2O4 NCs catalysts tested, the Ag loading of 0.98 wt% exhibited the highest catalytic activity toward hydrolysis of AB with a highly turnover frequency of TOF = 264 min−1 at room temperature, being higher than that of most reported Ag-based catalysts. Especially, these catalysts can be readily separated from the solution for recycle purpose, and can keep the high activity even after seven times of recycle. These results showed that Ag(0)/SiO2–CoFe2O4 NCs prepared in this study are a promising catalyst for hydrogen production from aqueous AB and for developing a highly efficient hydrogen storage system for fuel cell applications.A facile and effective approach has been applied for in situ fabrication of SiO2–CoFe2O4 supported well dispersed Ag nanoparticles, which exhibited the excellent catalytic activity for hydrogen generation from the hydrolysis of AB at room temperature.

Ultrafine non-noble bimetallic Cu–Co nanoparticles (∼2 nm) encapsulated within SiO2 nanospheres (Cu–Co@SiO2) have been successfully synthesized via a one-pot synthetic route in a reverse micelle system and characterized by SEM, TEM, EDS, XPS, PXRD, ICP, and N2 adsorption–desorption methods. In each core–shell Cu–Co@SiO2 nanosphere, several Cu–Co NPs are separately embedded in SiO2. Compared with their monometallic counterparts, the bimetallic core–shell nanospheres CuxCo1–x@SiO2 with different metal compositions show a higher catalytic performance for hydrogen generation from the hydrolysis of ammonia borane (NH3BH3, AB) at room temperature, due to the strain and ligand effects on the modification of the surface electronic structure and chemical properties of Cu–Co NPs in the SiO2 nanospheres. Especially, the Cu0.5Co0.5@SiO2 nanospheres show the best catalytic performance among all the synthesized CuxCo1–x@SiO2 catalysts in the hydrolytic dehydrogenation of AB. In addition, the activation energy (Ea) of Cu0.5Co0.5@SiO2 core–shell structured nanospheres for the hydrolysis of AB is estimated to be 24 ± 2 kJ mol–1, relatively low values among the bimetallic catalysts reported for the same reaction. Furthermore, the multi-recycle test shows that the bimetallic Cu0.5Co0.5@SiO2 core–shell nanospheres are still highly active for hydrolytic dehydrogenation of AB even after 10 runs, implying a good recycling stability in the catalytic reaction.

Fullerenol nanoparticles have intriguing potentials in biomedical applications. However, the structures, mechanisms of syntheses and mechanisms of antioxidant activities of fullerenols at the atomistic level, which substantialize their properties and applications, remain opened questions. Here, we review the syntheses, structures and antioxidant activities of fullerenols. Especially, we focus on the knowledge at the atomistic level. Experimentally, fullerenols can be synthesized using oxidation reactions in either acidic conditions or alkaline conditions. The latter reactions yield fullerenols with high hydroxyl numbers and better water solubility. For fullerenol structures, a precision structural model has been recently proposed for C60 fullerenols, which explain the experimentally-observed radical anion properties and pH-dependent infrared spectroscopic properties. Calculations have suggested that the most thermodynamically stable structures of many fullerenols have hydroxyls located aggregately in islands on the fullerene cages, although the most stable configuration of C60(OH)24 has hydroxyls distributed on C60 equator. Two different ·OH-scavenging mechanisms are possible for fullerenols. Fullerenols with low degrees of hydroxylation prefer the ·OH addition mechanism, whereas those with high degrees of hydroxylation prefer the hydrogen abstraction mechanism. The O2∙−-scavenging mechanism is related to redox potentials, charges and H-bond nets of the fullerenols.

•Ru@SiO2 core–shell NPs are synthesized via a simple one-pot synthetic route.•Ultrafine Ru NPs (∼2 nm) embedded in well-proportioned SiO2 nanospheres (∼25 nm).•Ru@SiO2 shows a high activity and good durability for H2 generation from NH3BH3.•The measured activation energy 38.2 kJ mol−1 is lower than most of the reported values.Ru@SiO2 core–shell structured nanospheres have been prepared via a one-pot synthetic route in a NP-5/cyclohexane reverse micelle system and characterized by XRD, SEM, TEM, N2 adsorption–desorption, and H2 temperature programmed desorption. The characterized results show that ultrafine Ru nanoparticles (NPs) of around 2 nm are effectively embedded in the center of well-proportioned spherical and porous silica nanospheres (∼25 nm in diameter). Interestingly, the number of Ru NPs increases inside the spherical particles of SiO2 as the increase of Ru loading. The as-synthesized Ru@SiO2 exhibits high catalytic activity and good durability for hydrogen generation from the aqueous of ammonia borane (AB) complex under ambient atmosphere at room temperature. The hydrolysis activation energy of Ru@SiO2 was estimated to be about 38.2 kJ mol−1, which is lower than most of the reported activation energy values for the same reaction using many different Ru-based and other noble metal containing catalysts, indicating the superior catalytic performance of these core–shell structured nanospheres.

•New Cu–Ni/MCM-41 catalysts are synthesized and used as catalyst for hydrolysis of AB.•Cu–Ni/MCM-41 exhibit superior activity than monometallic counterparts and pure bimetallic NPs.•The highest TOF value in Cu-based catalysts for hydrolysis of AB is obtained.•The measured activation energy 38 kJ mol−1 is lower than most of the reported values.Bimetallic Cu–Ni nanoparticles (NPs) were successfully immobilized in MCM-41 using a simple liquid impregnation-reduction method. All the resulting composites Cu–Ni/MCM-41 catalysts with various contents of Cu–Ni, and in particular Cu0.2Ni0.8/MCM-41 sample, outperform the activity of monometallic Cu and Ni counterparts and pure bimetallic Cu0.2Ni0.8 NPs in hydrolytic dehydrogeneration of ammonia borane (AB) at room temperature. The Cu0.2Ni0.8/MCM-41 catalyst exhibits excellent catalytic activity with a total turnover frequency (TOF) value of 10.7 mol H2 mol catalyst−1 min−1 and a low activation energy value of 38 kJ mol−1 at room temperature. In addition, Cu0.2Co0.8/MCM-41 also exhibits excellent activity with a TOF value as high as 15.0 mol H2 mol catalyst−1 min−1. This obtained activity represents the highest catalytic active of Cu-based monometallic and bimetallic catalysts up to now toward the hydrolytic dehydrogeneration of ammonia borane (AB). The unprecedented excellent activity has been successfully achieved thanks to the strong bimetallic synergistic effects among the Cu–Ni (or Co) NPs of the composites.

Reduced graphene oxide (RGO) supported copper nanoparticles (NPs) were synthesized via a facile in situ procedure using ammonia borane (AB) as a reductant. The as-prepared nanocatalysts exert satisfactory catalytic activity (3.61 mol H2 mol per catalyst per min), and appear to be the best Cu nanocatalysts up to now for the dehydrogenation of ammonia borane.

Based on the density-functional theory, geometric, energetic, electronic, and magnetic properties of phosphorus-doped small titanium clusters TinP (n = 1–12) have been investigated. For the ground state structures of Ti10P, Ti11P, and Ti12P clusters, the P atom completely fell into the center of the clusters forming the P-encapsulating Ti cage clusters. Doping of the P atom enhanced the stability of the Ti clusters. The binding energies, second-order energy differences, and fragmentation energies with the size of clusters showed Ti6P and Ti12P to be endowed with special stability. The total magnetic moments of TinP clusters exhibited odd–even staggering behavior. The quenching of the magnetic moment has not been found in TinP clusters. The density of states of clusters was discussed to understand the origin of peculiar magnetic properties.Graphical abstractHighlights► TinP (n = 1–12) clusters were investigated by DFT calculations. ► The P-encapsulating Tin cage clusters are found in Ti10P, Ti11P, and Ti12P. ► Ti6P and Ti12P clusters have special stability. ► The total magnetic moments of TinP clusters exhibited odd–even staggering behavior. ► Density of states of cluster was discussed to explore origin of magnetic property.

Diverse mesoporous CuO nanostructures have been prepared by a facile and scaleable wet-chemical method and reduced to mesoporous Cu nanostructures by using the reductant ammonia borane (AB). These mesoporous Cu nanostructures have been applied as a catalyst for hydrogen generation from the methanolysis of AB. The catalytic results show that the reaction rate and the amount of hydrogen evolution significantly relied on their morphologies. Compared with the nanosheet-like, bundle-like and dandelion-like Cu, the flower-like Cu nanostructures exhibit the highest catalytic activity with a total turnover frequency (TOF) value of 2.41 mol H2 mol catalyst−1 min−1 and a low activation energy value of 34.2 ± 1.2 kJ mol−1 at room temperature. Furthermore, the flower-like Cu nanostructures have also shown excellent activity in recycling tests. The low cost and high performance of Cu nanocatalysts may offer high potential for its practical application in hydrogen generation from the methanolysis of AB.

Ni nanoparticles modified with a Mo dopant have been synthesized on graphene sheets via a facile chemical reduction route, which show the highest catalytic activity reported to date for noble-metal-free catalysts for hydrogen evolution from the hydrolysis of ammonia borane with a turnover frequency value as high as 66.7 mol H2 (mol metal min)−1.

CeOx-modified RhNi nanoparticles (NPs) grown on reduced graphene oxide (rGO) (RhNi@CeOx/rGO) have been facilely prepared and successfully used as highly efficient catalysts for the rapid and complete hydrogen generation from aqueous solution of hydrazine borane (N2H4BH3) and hydrazine (N2H4), respectively. It was found that the CeOx-doped RhNi NPs with a size of around 3.5 nm were highly dispersed on rGO nanosheets. Among all the catalysts investigated, the optimized catalyst Rh0.8Ni0.2@CeOx/rGO with a CeOx content of 13.9 mol% exhibited the highest catalytic performance. The total turnover frequency (TOF) of Rh0.8Ni0.2@CeOx/rGO for hydrogen generation from N2H4BH3 reached 666.7 h−1 (molH2 mol(Rh+Ni)−1 h−1) at 323 K, which was among the highest of all the catalysts reported to date for this reaction, 10-fold higher than that of the benchmark catalyst Rh0.8Ni0.2, and 3-fold higher than that of Rh0.8Ni0.2 with a CeOx dopant (Rh0.8Ni0.2@CeOx) and a rGO support (Rh0.8Ni0.2/rGO). Even at room temperature, Rh0.8Ni0.2@CeOx/rGO can achieve a complete hydrogen generation from N2H4BH3 and N2H4 with a TOF value of 111.2 and 36.4 h−1. This excellent catalytic performance might be attributed to the synergistic structural and electronic effects of the RhNi NPs, CeOx dopant, and rGO support. Moreover, this general method can be easily extended to facile synthesis of other metal/rGO systems with the doping of rare-earth oxides for more applications.