Palladium deposition on copper(II) phthalocyanine/metal organic framework composite and electrocatalytic activity of the modified electrode towards the hydrogen evolution reaction

Monama, Gobeng R.; Mdluli, Siyabonga B.; Mashao, Gloria; Makhafola, Mogwasha D.; Ramohlola, Kabelo E.; Molapo, Kerileng M.; Hato, Mpitloane J.; Makgopa, Katlego; Iwuoha, Emmanuel I.; Modibane, Kwena D.

doi:10.1016/j.renene.2017.11.084

Cited by 66 publications

(54 citation statements)

References 53 publications

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“…Monama et al. used palladium and CuPc linked to a metal organic framework, which exhibited a Tafel slope of about 176.9 mV dec −1 with an exchange current density of 1 × 10 −4 mA cm −2 …”

Section: Resultsmentioning

confidence: 99%

Solution Processable Transition Metal Phthalocyanine Nanofibres

Madhuri

John

2019

ChemistrySelect

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Solution processable organic functional materials are highly desirable for device fabrication and applications. The insoluble nature of unsubstituted metal phthalocyanines (MPcs) often limits their applications that demand solution based coating techniques. In this work, nano‐architectures of metal phthalocyanines with important transition metal ions, Mn, Fe, Co, Cu and Zn that are highly dispersible in polar organic solvents have been prepared through a simple chemical route and applied as electrode materials for electrochemical hydrogen evolution reaction (HER). The formation of different MPcs is confirmed through various techniques such as Raman spectrocopy, X‐ray diffraction and X‐ray photoelectron spectroscopy. The morphology of the synthesized MPcs has a fibre‐like structure with varying dimensions of 150–650 nm in width and 5–10 μm in length. These nanostructures are supramolecular self‐assemblies of individual macrocycle rings coming together to form fibre‐like structures through π‐π interactions and are highly ordered with β crystal phase. The obtained CuPc and CoPc nanofibre dispersion coated on to a glassy carbon electrode exhibited an onset potential of −250 and −290 mV and a Tafel slope of 120 and 107 mV dec−1, respectively, for HER and good stability up to 1000 cycles.

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Section: Resultsmentioning

confidence: 99%

Solution Processable Transition Metal Phthalocyanine Nanofibres

Madhuri

John

2019

ChemistrySelect

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“…Decrease in platinum content with the increase in electrocatalytic activity was also reported for platinum nanoparticles dispersed on Ni(OH)2 [60][61][62], Ni3N [63] CoP [64], nitrogen-doped carbon/Ni nanofibers [65], nitrogen-doped ordered mesoporous carbon [66], sulfur-doped graphene [67] and Fe-doped α-Ni(OH)2 [68]. Similar synthetic procedures as those described in the preceding text were used for preparation of other supported PGMs or their alloys and composites with non-noble metals, including Pd@Cu(II) phthalocyanine/MOF [69], Ru nanoparticles supported on cobalt carbonate hydroxide nanowires [70], PtCu anchored on N-doped carbon nanofibers [71], and Co, Fe co-doped Ru on carbon [72]. Further improvement of electrocatalytic of supported metallic nanoparticles can also be achieved by the functionalization of Pt/CoP with ethylene glycol [64], with the specific activity of 101.2 mA μgPt -1 , and Rh with polyallylamine [73].…”

Section: Supported Metallic Nanoparticlesmentioning

confidence: 99%

“…Hydrogen atom spillover (not to be confused with H2 spillover, which includes dissociation and is an important step for hydrogenation reactions and hydrogen storage) was recognized as phenomenon responsible for the promotion of Pt electrocatalytic activity towards the hydrogen evolution 47 years ago, for Pt supported on pyrolytic graphite [144]. Several experimental works contributed to the affirmation of Hads spillover as the important step in HER mechanism at Pt/C [145], Pt/transition-metal-oxide [146], Pt/Au [147], Pi/Ni [148], atomically-dispersed-Pt/WO3-x [149], Pd/Au [150], WO3·2H2O/WS2 [151], Rh/MoS2 [152], Rh/Si (although authors do not employ the term spillover) [153], Pd@Cu(II) phthalocyanine/MOF [69], and Ni/rGO interfaces [154,155]. Kinetic Monte-Carlo simulations were employed to investigate the impact of spillover rate on the rate of H2 production at Ni/rGO interface, using the model that was able to qualitatively reproduce the experimentally observed trends [155].…”

Section: Role Of the Metal-support Interfaces In Her Mechanismmentioning

confidence: 99%

Hydrogen Evolution Reaction - From Single Crystal to Single Atom Catalysts

Gutić¹,

Dobrota²,

Fako³

et al. 2020

Preprint

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Hydrogen evolution reaction (HER) is one of the most important reaction in electrochemistry. This is not only because it is the simplest way to produce high purity hydrogen and the fact that it is the side reaction in many other technologies. HER actually shaped current electrochemistry because it was in focus of active research for so many years (and it still is). The number of catalysts investigated for HER is immense, and it is impossible to overview them all. In fact, it seems that the complexity of the field overcomes the complexity of HER. The aim of this review is to point out some of the latest developments in HER catalysis, current directions and some of the missing links between a single crystal, nanosized supported catalysts and, recently emerging, single atom catalysts for HER.3 of 36 HER at single crystal surfaces and bulk surfacesA crystalline solid can be considered as a series of mutually parallel lattice planes, arranged in a periodic way. Close to the surface, the spatial arrangement of the lattice planes, their crystallographic structure, as well as the dynamics of the constituent atoms may differ from the corresponding features in the bulk [1]. Most clean metals show the tendency to minimize their surface energy. One of the mechanisms is relaxation, the shift of one or more lattice planes located near to the surface, usually perpendicularly to the surface, so that the interlayer distance changes compared to the bulk lattice. The other one is reconstruction -change in equilibrium positions and bonding of surface atoms so that the projection of bulk unit cell to the given surface does not correspond to the surface unit cell. Different crystallographic planes (with different Miller indices) of the same metal exhibit unequal surface densities (number of atoms per surface area), and therefore undergo surface relaxation/reconstruction to different extents [2]. For example, Pt(100) has lower surface density compared to densely packed Pt(111) and therefore has a stronger tendency to relax/reconstruct. Since the main driving force for the mentioned surface modifications is the low coordination number (non-saturation) of surface atoms, it is obvious that atom/molecule adsorption on clean metal surfaces can have a significant effect on its surface structure, inducing relaxation/reconstruction changes. This is of huge importance for HER, as it involves adsorbed atomic hydrogen (Hads) as an intermediate. Additionally, in an electrochemical system, the electrode will be modified by adsorption of "spectator" species (ions/molecules from the electrolyte), so HER will not be taking place on clean metal surfaces, but rather on modified ones. Obviously, there is a complex dynamic interplay between the catalyst surface, reactants, intermediates, and electrolyte.According to the Sabatier principle, the interaction of the reaction reactants/intermediates with the catalyst has to be optimal in strength. If it is too weak, the reactants will not bind to the catalyst and the reaction will not be able to take place. In...

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“…It should be noted that Pd was broadly used as an electro‐catalyst in alkaline media than that acidic ones . Also, it is noticeable that Pd has lower electro‐catalytic activity than Pt; however it can be acts as an appropriate substitute to enhance the electro‐catalytic activity by application of bimetallic nanostructures such as Pd‐Au, Pd‐Ru, PtM (M=Pd, Ir) and Pd‐Cu . The increased performance of the Pd−Cu is due to structure and conceivable synergetic effect of Pd and Cu components and/or electronic and structural effects by addition of the certain metal in Pd …”

Section: Introductionmentioning

confidence: 99%

“…[13][14][15] Also, it is noticeable that Pd has lower electro-catalytic activity than Pt; however it can be acts as an appropriate substitute to enhance the electro-catalytic activity by application of bimetallic nanostructures such as Pd-Au, [16] Pd-Ru, [17] PtM (M = Pd, Ir) [18] and Pd-Cu. [19][20][21] The increased performance of the PdÀ Cu is due to structure and conceivable synergetic effect of Pd and Cu components and/or electronic and structural effects by addition of the certain metal in Pd. [22,23] In other aspect, surfactants having amphiphilic structures are a class of molecules that form thermodynamically stable aggregates of inherently nanoscale dimensions both in solution and interfaces.…”

Section: Introductionmentioning

confidence: 99%

Fabrication and Performance Evaluation of Pd‐Cu Nanoparticles for Hydrogen Evolution Reaction

Hosseini

Ghasemi

2019

ChemistrySelect

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Herein, the effects of different types of surfactants including sodium dodecyl sulfate (SDS), cetyltrimethyl ammonium bromide (CTAB), and t‐octyl phenoxy polyethoxy ethanol (Triton X‐100, TX‐100) were presented on the hydrogen evolution reaction (HER) at the surface of carbon paste electrode (CPE) modified with Pd−Cu nanoparticles. Firstly, Cu nanoparticles with average diameters at about 80 nm were electro‐deposited at the CPE surface in H2SO4 solution containing CTAB and CuSO4 by potentiostatic method. Then, Pd−Cu bimetallic nanoparticles with diameters at about 75 nm were prepared through galvanic replacement reaction between PdII ions and Cu particles. The synthesized Cu nanoparticles were covered by CTAB in solution and surface tension of the nanoparticles were decreased, and consequently stabilized. Also, the surfactants play different roles on the HER depending on the electrode polarity and surface charges. The electro‐catalytic activity of the Pd−Cu/CPE and nano‐Cu/CPE towards HER was found to be highest in the presence of SDS. The effects of galvanic replacement reaction and type of surfactants on kinetic parameters of the HER such as cathodic electron transfer coefficient and exchange current density were comparatively investigated.

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Palladium deposition on copper(II) phthalocyanine/metal organic framework composite and electrocatalytic activity of the modified electrode towards the hydrogen evolution reaction

Cited by 66 publications

References 53 publications

Solution Processable Transition Metal Phthalocyanine Nanofibres

Solution Processable Transition Metal Phthalocyanine Nanofibres

Hydrogen Evolution Reaction - From Single Crystal to Single Atom Catalysts

Fabrication and Performance Evaluation of Pd‐Cu Nanoparticles for Hydrogen Evolution Reaction

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