Palladium nanoparticles supported on amine-functionalized alginate foams for hydrogenation of 3-nitrophenol

  • Shengye Wang
  • Yayuan Mo
  • Thierry Vincent
  • Jean-Claude Roux
  • Enrique Rodríguez-Castellón
  • Catherine Faur
  • Eric GuibalEmail author
Chemical routes to materials


A new material, consisting of alginate–polyethyleneimine (AP) foam, with high percolating properties has been designed for palladium recovery in fixed-bed reactor. The foam, having high affinity for Pd(II), can be also used for manufacturing heterogeneous hydrogenation catalyst. SEM–EDX and TEM analyses were performed to determine the structure of the foams and the distribution of Pd nanoparticles (after metal reduction). Metal-sorbent interactions and oxidation state of Pd are characterized by XPS. Pd(0)-bearing foams are investigated for the hydrogenation of 3-nitrophenol (3-NP) using HCOOH as the hydrogen donor. The maximum sorption capacity of Pd(II) by AP foams reaches up to 224 mg g−1. The water flux (under water-depth pressure of 6 mbar) reaches 24.8 mL cm−2 min−1 (superficial flow velocity: 14.9 m h−1). The foams are remarkably stable: The mass loss under strong shaking for 2 days does not exceed 3%. For catalytic application, Pd loading conditions were optimized (flow rate, metal concentration) to reach 101 mg Pd g−1 (97% metal removal). Under these conditions, Pd overloading and nanoparticles aggregation can be minimized. The catalytic hydrogenation of 3-nitrophenol (using formic acid as the hydrogen donor) was optimum for a HCOOH/3-NP molar ratio close to 160 (pH between 3 and 4). High flow rates minimize diffusion effects; the apparent rate constant (for pseudo-first-order rate equation) reaches 9.7 × 10−3 s−1. The reuse of the foams over 30 cycles shows the long-term stability of catalytic activity. The test on continuous (one-pass) mode shows a progressive poisoning of the catalyst. However, a simple washing with water is sufficient for recovering catalytic activity.



S. Wang (CSC, Grant No. 20156660002) and Y. Mo (CSC, Grant No. 201708450080) acknowledge the China Scholarship Council for providing PhD fellowship. E. Rodríguez-Castellón thanks to project RTI2018-099668-B-C22 (Ministerio de Ciencia, Innovación y Universidades of Spain) project UMA18-FEDERJA-126 of Junta de Andalucía (Spain) and FEDER fund.

Supplementary material

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Supplementary material 1 (DOCX 2176 kb)


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Authors and Affiliations

  1. 1.C2MA, IMT Mines AlesUniv MontpellierAlesFrance
  2. 2.Department of Environmental Engineering, College of Chemistry and Environmental EngineeringShenzhen UniversityShenzhenPeople’s Republic of China
  3. 3.Departamento de Química Inorgánica, Facultad de CienciasUniversidad de MálagaMálagaSpain
  4. 4.IEM, Institut Européen des MembranesUniv Montpellier, CNRS, ENSCMMontpellierFrance

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