Special Issue "Direct Synthesis of Hydrogen Peroxide"

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalytic Materials".

Deadline for manuscript submissions: closed (15 January 2019)

Special Issue Editors

Guest Editor
Prof. Dr. Giorgio Strukul

Department of Molecular Sciences and Nano Systems, Università Ca’ Foscari Venezia, Via Torino 155, 30172 Mestre Venezia, Italy
Website | E-Mail
Interests: transition metal catalysis; noble metal systems; oxidation reactions; sustainability; alternative solvent systems
Guest Editor
Dr. Federica Menegazzo

Department of Molecular Sciences and Nano Systems, Università Ca’ Foscari Venezia, Via Torino 155, 30172 Mestre Venezia, Italy
Website 1 | Website 2 | E-Mail
Interests: heterogeneous catalysis; metal nanoparticles; oxidation reactions; industrial processes; biomass valorization

Special Issue Information

Dear Colleagues,

In the past 10-15 years hydrogen peroxide has experienced a constant increase in production with some 5 Mton being expected by the end of 2017. Environmental regulations have played a vital role in popularizing the use of H2O2 over other oxidants, by virtue of the chemical being emission-free and eco-friendly in nature. Hydrogen peroxide’s robust growth could be traced back to the overwhelming support of the environmental protection authorities and tightening effluent regulations in almost every application area. However, the current hydrogen peroxide production is still almost exclusively based on the anthraquinone process, while the long-sought alternative direct synthesis from hydrogen and oxygen has been the subject of extensive investigation. This special issue collects original research papers, reviews and commentaries focused on the still open challenges for the direct synthesis of H2O2. Submissions are welcome especially in (but not limited to) the following areas:

  • Development of newly designed catalysts (metals, alloys, effects of acidity and additives)
  • Process development (reaction conditions, explosive or non explosive regimes, etc.)
  • Non catalytic methods
  • Innovative reactor design (microreactors, membrane reactors, trickle-bed reactors, etc.)
  • In situ production and use
  • Mechanistic investigations

Prof. Dr. Giorgio Strukul
Dr. Federica Menegazzo
Guest Editors

Manuscript Submission Information

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Keywords

  • hydrogen peroxide direct synthesis
  • hydrogen
  • oxygen
  • metal catalysts
  • alloy catalysts
  • microreactors
  • membrane reactors
  • trickle-bed reactors
  • mechanistic studies

Published Papers (4 papers)

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Research

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Open AccessArticle Direct Synthesis of Hydrogen Peroxide under Semi-Batch Conditions over Un-Promoted Palladium Catalysts Supported by Ion-Exchange Sulfonated Resins: Effects of the Support Morphology
Catalysts 2019, 9(2), 124; https://doi.org/10.3390/catal9020124
Received: 10 December 2018 / Revised: 14 January 2019 / Accepted: 16 January 2019 / Published: 31 January 2019
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Abstract
Palladium catalysts supported by a mesoporous form of sulfonated poly-divinylbenzene, Pd/µS-pDVB10 (1%, w/w) and Pd/µS-pDVB35 (3.6% w/w), were applied to the direct synthesis of hydrogen peroxide from dihydrogen and dioxygen. The reaction was carried for 4 h [...] Read more.
Palladium catalysts supported by a mesoporous form of sulfonated poly-divinylbenzene, Pd/µS-pDVB10 (1%, w/w) and Pd/µS-pDVB35 (3.6% w/w), were applied to the direct synthesis of hydrogen peroxide from dihydrogen and dioxygen. The reaction was carried for 4 h out in a semibatch reactor with continuous feed of the gas mixture (H2/O2 = 1/24, v/v; total flow rate 25 mL·min−1), at 25 °C and 101 kPa. The catalytic performances were compared with those of a commercial egg-shell Pd/C catalyst (1%, w/w) and of a palladium catalyst supported by a macroreticular sulfonated ion-exchange resin, Pd/mS-pSDVB10 (1%, w/w). Pd/µS-pDVB10 and Pd/C showed the highest specific activity (H2 consumption rate of about 75–80 h−1), but the resin supported catalyst was much more selective (ca 50% with no promoters). The nanoparticles (NP) size was somewhat larger in Pd/µS-pDVB10, showing that either the reaction was structure insensitive or diffusion limited to some extent over Pd/C, in which the support is microporous. The open pore structure of Pd/µS-pDVB10, possibly ensuring the fast removal of H2O2 from the catalyst, could also be the cause of the relatively high selectivity of this catalyst. In summary, Pd/µS-pDVB10 was the most productive catalyst, forming ca 375 molH2O2·kgPd−1·h−1, also because it retained a constant selectivity, while the other ones underwent a more or less pronounced loss of selectivity after 80–90 min. Ageing experiments showed that for a palladium catalyst supported on sulfonated mesoporous poly-divinylbenzene storage under oxidative conditions implied some deactivation, but a lower drop in the selectivity; regeneration upon a reductive treatment or storage under strictly anaerobic conditions (dry-box) lead to an increase of the activity but to both a lower initial selectivity and a higher drop of selectivity with time. Full article
(This article belongs to the Special Issue Direct Synthesis of Hydrogen Peroxide)
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Open AccessArticle Experimental Evaluation of a Membrane Micro Channel Reactor for Liquid Phase Direct Synthesis of Hydrogen Peroxide in Continuous Flow Using Nafion® Membranes for Safe Utilization of Undiluted Reactants
Catalysts 2018, 8(11), 556; https://doi.org/10.3390/catal8110556
Received: 28 October 2018 / Revised: 12 November 2018 / Accepted: 13 November 2018 / Published: 17 November 2018
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Abstract
In recent years, various modular micro channel reactors have been developed to overcome limitations in challenging chemical reactions. Direct synthesis of hydrogen peroxide from hydrogen and oxygen is a very interesting process in this regard. However, the complex triphasic process (gaseous reactants, reaction [...] Read more.
In recent years, various modular micro channel reactors have been developed to overcome limitations in challenging chemical reactions. Direct synthesis of hydrogen peroxide from hydrogen and oxygen is a very interesting process in this regard. However, the complex triphasic process (gaseous reactants, reaction in liquid solvent, solid catalyst) still holds challenges regarding safety, selectivity and productivity. The membrane micro reactor system for continuous liquid phase H2O2 direct synthesis was designed to reduce safety issues by separate dosing of the gaseous reactants via a membrane into a liquid-flow channel filled with a catalyst. Productivity is increased by enhanced mass transport, attainable in micro channels and by multiple re-saturation of the liquid with the reactants over the length of the reaction channel. Lastly, selectivity is optimized by controlling the reactant distribution. The influence of crucial technical features of the design, such as micro channel geometry, were studied experimentally in relationship with varying reaction conditions such as residence time, pressure, reactant ratio and solvent flow rate. Successful continuous operation of the reactor at pressures up to 50 bars showed the feasibility of this system. During the experiments, control over the reactant ratio was found to be crucial in order to maximize product yield. Thereby, yields above 80% were achieved. The results obtained are the key elements for future development and optimization of this reactor system, which will hopefully lead to a breakthrough in decentralized H2O2 production. Full article
(This article belongs to the Special Issue Direct Synthesis of Hydrogen Peroxide)
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Review

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Open AccessReview Boosting the Characterization of Heterogeneous Catalysts for H2O2 Direct Synthesis by Infrared Spectroscopy
Catalysts 2019, 9(1), 30; https://doi.org/10.3390/catal9010030
Received: 30 November 2018 / Revised: 18 December 2018 / Accepted: 19 December 2018 / Published: 2 January 2019
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Abstract
Infrared (IR) spectroscopy is among the most powerful spectroscopic techniques available for the morphological and physico-chemical characterization of catalytic systems, since it provides information on (i) the surface sites at an atomic level, (ii) the nature and structure of the surface or adsorbed [...] Read more.
Infrared (IR) spectroscopy is among the most powerful spectroscopic techniques available for the morphological and physico-chemical characterization of catalytic systems, since it provides information on (i) the surface sites at an atomic level, (ii) the nature and structure of the surface or adsorbed species, as well as (iii) the strength of the chemical bonds and (iv) the reaction mechanism. In this review, an overview of the main contributions that have been determined, starting from IR absorption spectroscopy studies of catalytic systems for H2O2 direct synthesis, is given. Which kind of information can be extracted from IR data? IR spectroscopy detects the vibrational transitions induced in a material by interaction with an electromagnetic field in the IR range. To be IR active, a change in the dipole moment of the species must occur, according to well-defined selection rules. The discussion will be focused on the advancing research in the use of probe molecules to identify (and possibly, quantify) specific catalytic sites. The experiments that will be presented and discussed have been carried out mainly in the mid-IR frequency range, between approximately 700 and 4000 cm−1, in which most of the molecular vibrations absorb light. Some challenging possibilities of utilizing IR spectroscopy for future characterization have also been envisaged. Full article
(This article belongs to the Special Issue Direct Synthesis of Hydrogen Peroxide)
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Open AccessReview Recent Advances in the Direct Synthesis of Hydrogen Peroxide Using Chemical Catalysis—A Review
Catalysts 2018, 8(9), 379; https://doi.org/10.3390/catal8090379
Received: 1 August 2018 / Revised: 26 August 2018 / Accepted: 28 August 2018 / Published: 5 September 2018
Cited by 1 | PDF Full-text (2183 KB) | HTML Full-text | XML Full-text
Abstract
Hydrogen peroxide is an important chemical of increasing demand in today’s world. Currently, the anthraquinone autoxidation process dominates the industrial production of hydrogen peroxide. Herein, hydrogen and oxygen are reacted indirectly in the presence of quinones to yield hydrogen peroxide. Owing to the [...] Read more.
Hydrogen peroxide is an important chemical of increasing demand in today’s world. Currently, the anthraquinone autoxidation process dominates the industrial production of hydrogen peroxide. Herein, hydrogen and oxygen are reacted indirectly in the presence of quinones to yield hydrogen peroxide. Owing to the complexity and multi-step nature of the process, it is advantageous to replace the process with an easier and straightforward one. The direct synthesis of hydrogen peroxide from its constituent reagents is an effective and clean route to achieve this goal. Factors such as water formation due to thermodynamics, explosion risk, and the stability of the hydrogen peroxide produced hinder the applicability of this process at an industrial level. Currently, the catalysis for the direct synthesis reaction is palladium based and the research into finding an effective and active catalyst has been ongoing for more than a century now. Palladium in its pure form, or alloyed with certain metals, are some of the new generation of catalysts that are extensively researched. Additionally, to prevent the decomposition of hydrogen peroxide to water, the process is stabilized by adding certain promoters such as mineral acids and halides. A major part of today’s research in this field focusses on the reactor and the mode of operation required for synthesizing hydrogen peroxide. The emergence of microreactor technology has helped in setting up this synthesis in a continuous mode, which could possibly replace the anthraquinone process in the near future. This review will focus on the recent findings of the scientific community in terms of reaction engineering, catalyst and reactor design in the direct synthesis of hydrogen peroxide. Full article
(This article belongs to the Special Issue Direct Synthesis of Hydrogen Peroxide)
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