Bottom-Up Assembly of Ni<sub>2</sub>P Nanoparticles into Three-Dimensional Architectures: An Alternative Mechanism for Phosphide Gelation

Hitihami‐Mudiyanselage, Asha; Senevirathne, Keerthi; Brock, Stephanie L.

doi:10.1021/cm5030958

Cited by 31 publications

(40 citation statements)

References 36 publications

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“…[16][17][18][19] This same line of theory driven inquiry led to the investigation of transition metal phosphides as a new class of materials with excellent catalytic activity for HER and high stability in acidic media. Research efforts over the past decade have explored many aspects of these materials including synthetic methodology and mechanisms 20,21,30,[22][23][24][25][26][27][28][29] , the effects of varying atomic composition [31][32][33][34] , nano-structuring [35][36][37] , and computational modeling of their catalytically active surface sites. 31,[38][39][40][41][42][43][44] Despite great progress in developing this class of materials, earth abundant alternatives still present orders of magnitude lower activity than their precious metal counterparts.…”

Section: Introductionmentioning

confidence: 99%

Covalent Functionalization of Nickel Phosphide Nanocrystals with Aryl-Diazonium Salts

et al. 2021

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Covalent functionalization of Ni2P nanocrystals was demonstrated using aryl-diazonium salts. Spontaneous adsorption of aryl functional groups was observed, with surface coverages ranging from 20-96% depending on the native reactivity of the salt as determined by the aryl substitution pattern. Increased coverage was possible for low reactivity species using a sacrificial reductant. Functionalization was confirmed using thermogravimetric analysis, FTIR and X-ray photoelectron spectroscopy. The structure and energetics of this nanocrystal electrocatalyst system, as a function of ligand coverage, was explored with density functional theory calculations. The Hammett parameter of the surface functional group was found to linearly correlate with the change in Ni and P core-electron binding energies and the nanocrystal's work-function. The electrocatalytic activity and stability of the functionalized nanocrystals for hydrogen evolution were also improved when compared to the unfunctionalized material, but a simple trend based on electrostatics was not evident.

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Section: Introductionmentioning

confidence: 99%

Covalent Functionalization of Nickel Phosphide Nanocrystals with Aryl-Diazonium Salts

et al. 2021

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“…), [97][98][99][100][101] their oxides (TiO 2 , [102][103][104][105][106] Y 2 O 3 , [81] BaTiO 3 , [82] InTaO 4 , [107] SrTiO 3 , [87] Y 3 Al 5 O 12 , [108] etc. ), nitrides (Cu 3 N), [83] phosphides (InP, Ni 2 P) [85,109] and fluorides (GdF 3 ) [108] as well as combinations thereof (Fig. 8).…”

Section: Disordered Porous Structuresmentioning

confidence: 99%

“…There are a variety of chemical and physical stimuli that can be used for this purpose. Controlled destabilization can be accomplished by means of additives such as acids, bases, electrolytes, [99,110] complexing agents, [96,[114][115][116] ligand strippers, [85,88,97] or non-solvents. [82,[102][103][104][105]108] Another possibility is the use of non-additive triggers such as temperature, [82,83,100,[102][103][104][105] irradiation, [84,106] mechanical methods such as centrifugation, [81,107,117] ultrasonic treatment, [82] or electrochemical methods.…”

Section: Disordered Porous Structuresmentioning

confidence: 99%

Colloidal Nanocrystals: A Toolbox for Materials Chemistry

Matter

Niederberger

Putz

2021

Chimia

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Colloidal nanocrystals are the ideal building blocks for the fabrication of functional materials. Using various assembly, patterning or processing techniques, the nanocrystals can be arranged with unprecedented flexibility in 1-, 2- or 3-dimensional architectures over several orders of length scales, providing access to ordered or disordered, porous or non-porous, and simple as well as hierarchical structures. Careful selection of colloidal nanocrystals allows the properties of the final materials to be predefined. Moreover, by combining different nanocrystals, these properties can be fine-tuned for a specific application, opening up fascinating opportunities to create new materials for energy storage and conversion, catalysis, photocatalysis, biomedicine or optics. Indeed, functional materials made of preformed nanoparticles have been realized for metals, polymers, semiconductors, and ceramics, as well as for composites and organic-inorganic hybrids. In this review article, we introduce some concepts for the fabrication of colloidal nanocrystals and their assembly into dense and porous 3-dimensional structures. Porosity is a particularly important material property that strongly influences its application potential. Therefore, we pay special attention to this aspect and compare porous materials synthesized from nanoparticles with those from molecular routes. An additional focus is set on the degree of structural order that can be achieved on different length scales.

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“…The main cornerstones are the original oxidative removal of NC surface ligands 9 − 12 by methods like pH-dependent techniques, 13 use of specific ligands linked together by metal cation complexes, 14 light-induced gelation, 15 rapid freezing of NC solutions, 4 and nonoxidative ligand removal by trivalent cations. 1 Likewise, the catalogue of different materials that could be synthesized as NCs and assembled into gel-like networks has been expanded starting with different semiconductors, for example, CdSe, CdS, PbS, or ZnS, 12 and metal oxides, 16 , 17 phosphides, 18 , 19 and nitrides, 20 as well as noble metal NCs. 21 , 22 The potential applications of NC-based network structures range from electro- 23 − 26 and photocatalysis 27 − 31 to (spectro)electrochemical sensing 32 , 33 and even thermoelectric applications.…”

Section: Introductionmentioning

confidence: 99%

Control over Structure and Properties in Nanocrystal Aerogels at the Nano-, Micro-, and Macroscale

2020

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Conspectus The assembly of individual colloidal nanocrystals into macroscopic solvogels and aerogels introduced a new exciting type of material into the class of porous architectures. In these so-called nanocrystal gels, the structure and properties can be controlled and fine-tuned to the smallest details. Recently it was shown that by employing nanocrystal building blocks for such gel materials, the interesting nanoscopic properties can be conserved or even expanded to properties that are available neither in the nanocrystals nor in their respective bulk materials. In general, the production of these materials features the wet-chemical synthesis of stable nanocrystal colloids followed by their carefully controlled destabilization to facilitate arrangement of the nanocrystals into highly porous, interconnected networks. By isolation of the synthesis of the discrete building blocks from the assembly process, the electronic structure, optical properties, and structural morphology can be tailored by the myriad of procedures developed in colloidal nanocrystal chemistry. Furthermore, knowledge and control over the structure–property correlation in the resulting gel structures opens up numerous new ways for extended and advanced applications. Consequently, the amount of different materials converted to nanocrystal-based gel structures is rising steadily. Meanwhile the number of methods for assembly initiation is likewise increasing, offering control over the overall network structure and porosity as well as the individual nanocrystal building block connection. The resulting networks can be dried by different methods to obtain highly porous air-filled networks (aerogels) or applied in their wet form (solvogels). By now a number of different applications profiting from the unique advantages of nanocrystal-based gel materials have been realized and exploited in the areas of photocatalysis, electrocatalysis, and sensing. In this Account, we aim to summarize the efforts undertaken in the structuring of nanocrystal-based network materials on different scales, fine-tuning of the individual building blocks on the nanoscale, the network connections on the microscale, and the macroscale structure and shape of the final construct. It is exemplarily demonstrated how cation exchange reactions (at the nanoscale), postgelation modifications on the nanocrystal networks (microscale), and the structuring of the gels via printing techniques (macroscale) endow the resulting nanocrystal gel networks with novel physicochemical, mechanical, and electrocatalytic properties. The methods applied in the more traditional sol–gel chemistry targeting micro- and macroscale structuring are also reviewed, showing their future potential promoting the field of nanocrystal-based aerogels and their applications.

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Bottom-Up Assembly of Ni₂P Nanoparticles into Three-Dimensional Architectures: An Alternative Mechanism for Phosphide Gelation

Cited by 31 publications

References 36 publications

Covalent Functionalization of Nickel Phosphide Nanocrystals with Aryl-Diazonium Salts

Covalent Functionalization of Nickel Phosphide Nanocrystals with Aryl-Diazonium Salts

Colloidal Nanocrystals: A Toolbox for Materials Chemistry

Control over Structure and Properties in Nanocrystal Aerogels at the Nano-, Micro-, and Macroscale

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Bottom-Up Assembly of Ni2P Nanoparticles into Three-Dimensional Architectures: An Alternative Mechanism for Phosphide Gelation

Cited by 31 publications

References 36 publications

Covalent Functionalization of Nickel Phosphide Nanocrystals with Aryl-Diazonium Salts

Covalent Functionalization of Nickel Phosphide Nanocrystals with Aryl-Diazonium Salts

Colloidal Nanocrystals: A Toolbox for Materials Chemistry

Control over Structure and Properties in Nanocrystal Aerogels at the Nano-, Micro-, and Macroscale

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Product

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Bottom-Up Assembly of Ni₂P Nanoparticles into Three-Dimensional Architectures: An Alternative Mechanism for Phosphide Gelation