Effect of size and oxidation state of size-controlled rhodium nanoparticles on the aqueous-phase hydrodechlorination of 4-chlorophenol

Baeza, J.A.; Calvo, L.; Gilarranz, Miguel Á.; Rodrı́guez, Juan J.

doi:10.1016/j.cej.2013.11.091

Cited by 58 publications

(44 citation statements)

References 48 publications

(68 reference statements)

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“…A number of authors have concluded that HDC is a structure sensitive reaction [9][10][11][12][13][14][15] although there is no general agreement on this issue [16]. In our previous works, dealing with monometallic Pd and Rh nanoparticles, we reported structure sensitiveness with evident dependence of activity and TOF on nanoparticle size [17][18][19].…”

Section: Introductionmentioning

confidence: 85%

“…In our previous works [17,18], non-supported monometallic Pd and Rh NPs were used as catalysts models in the aqueous phase HDC of 4-chlorophenol (4-CP), in order to gain insight into the effect of size and oxidation state of the metal NPs on activity/selectivity in the absence of support. Differences between both metals have been addressed, such as the specific hydrogenation ability (negligible in the case of PVP-based Pd NPs) or the effect of the electrodeficient to zerovalent species ratio on the activity within the ranges tested.…”

Section: Introductionmentioning

confidence: 99%

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Activity enhancement and selectivity tuneability in aqueous phase hydrodechlorination by use of controlled growth Pd-Rh nanoparticles

Baeza

Calvo

Rodrı́guez

et al. 2015

Applied Catalysis B: Environmental

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Section: Introductionmentioning

confidence: 85%

Section: Introductionmentioning

confidence: 99%

Activity enhancement and selectivity tuneability in aqueous phase hydrodechlorination by use of controlled growth Pd-Rh nanoparticles

Baeza

Calvo

Rodrı́guez

et al. 2015

Applied Catalysis B: Environmental

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“…Commonly used capping agents are polyvinylpirrolydone (PVP), polyvinylalcohol (PVA) and polyethyleneglycol (PEG), among others. The type and concentration of both reducing agent and capping agent are reported to have influence on the NP size [8,[25][26][27]. Moreover, the role of the remaining capping agent after synthesis in the catalyst performance is still controversial.…”

Section: Introductionmentioning

confidence: 99%

“…The most relevant are those related to the active phase, i.e. nanoparticles (NPs) size [5][6][7][8] and shape [9][10][11][12], and to the support, mainly pore size [13][14][15][16] and surface chemistry [17][18][19][20], but also the way of catalysts synthesis can affect the activity and/or selectivity [21,22].…”

Section: Introductionmentioning

confidence: 99%

Catalysts based on large size-controlled Pd nanoparticles for aqueous-phase hydrodechlorination

Baeza

Calvo

Rodrı́guez

et al. 2016

Chemical Engineering Journal

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“…Many methods have been used to prepare nanoparticles, including chemical reduction, thermal decomposition, metal vapor deposition, and electrochemical synthesis. 6,7 Size control of nanoparticles has been achieved in wet chemical reduction by the sophisticated and rigid control of several factors, including the solvent, 2,8 reactant concentrations, 9 additives, 10 pH, 11 and preparation temperature. 12 In this method, high-boiling-point alcohols such as polyols are often used to reduce metal cations in the presence of polymers that inhibit aggregation of the nanoparticles and stabilize metals in colloids because the boiling points of the polyols are higher than the temperatures required to reduce the metal cations.…”

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Facile Synthesis of Size-controlled Rh Nanoparticles via Microwave-assisted Alcohol Reduction and Their Catalysis of CO Oxidation

et al. 2017

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Size-controlled Rh nanoparticles stabilized by poly(vinylpyrrolidone) were quickly synthesized via alcohol reduction. Microwave-assisted synthesis in closed vessels allowed alcohols with low-to-high boiling points to be used as reductants under the same preparation conditions. Pure ethanol has not been used previously because its boiling point is lower than the temperature required for Rh 3+ reduction. Alcohols with relatively strong reduction ability were found to lead to smaller Rh nanoparticles. The ability to oxidize CO was enhanced as the Rh particle size decreased. additives, 10 pH, 11 and preparation temperature. 12 In this method, high-boiling-point alcohols such as polyols are often used to reduce metal cations in the presence of polymers that inhibit aggregation of the nanoparticles and stabilize metals in colloids because the boiling points of the polyols are higher than the temperatures required to reduce the metal cations. In contrast, the boiling points of monovalent alcohol including a small number of carbon such as ethanol are lower than the temperatures required to reduce metal cations such as Ru 3+ , Rh 3+, and Pd 2+ . To enable the use of low-boiling-point alcohols, the alcohols are mixed with water to increase the boiling point, and reduction is performed under reflux 13 or solvothermal 6 conditions. On the other hand, heating the alcohols with a conventional electric heater is slow and produces heterogeneous temperatures; thus, it takes a long time to prepare nanoparticles, and nanometals with a wide particle-size distribution are obtained. 14 Furthermore, because of differences in the equipment and physicochemical properties of the alcohol, the influence of the reduction ability of low-and high-boiling-point alcohols on the synthesis of nanoparticles has not been investigated under the same preparation conditions.In this study, we prepared Rh nanoparticles using different kinds of alcohols, including low-and high-boiling-point alcohols, as reductants under the same preparation conditions. The experimental design was enabled by using a microwaveassisted alcohol reduction method in a closed vessel, in which rapid and homogeneous heating and solvothermal conditions were achieved. We were thereby able to easily synthesize sizecontrolled Rh nanoparticles within 20min under the same preparation conditions. The average diameters of the nanoparticles, stabilized in poly(vinylpyrrolidone) (PVP), were 3.3 10.9 nm. The amount of PVP, a crucial determinant of catalytic activity, varied over a small range (72.384.1 wt %). 15 We discovered that the Rh particle size was dependent on the reduction ability of the alcohol. We also studied the particle size dependence of the CO oxidation ability of the Rh nanoparticles, because Rh is known to be an excellent catalyst for the oxidation of CO in car exhaust gas.Rh nanoparticles with different sizes were prepared by microwave-assisted alcohol reduction. Initially, RhCl 3 ¢3H 2 O as the metal precursor and PVP as the stabilizer were dissolved in either ethanol, e...

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Effect of size and oxidation state of size-controlled rhodium nanoparticles on the aqueous-phase hydrodechlorination of 4-chlorophenol

Cited by 58 publications

References 48 publications

Activity enhancement and selectivity tuneability in aqueous phase hydrodechlorination by use of controlled growth Pd-Rh nanoparticles

Activity enhancement and selectivity tuneability in aqueous phase hydrodechlorination by use of controlled growth Pd-Rh nanoparticles

Catalysts based on large size-controlled Pd nanoparticles for aqueous-phase hydrodechlorination

Facile Synthesis of Size-controlled Rh Nanoparticles via Microwave-assisted Alcohol Reduction and Their Catalysis of CO Oxidation

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