Diamond porous membranes: A material toward analytical chemistry

https://doi.org/10.1016/j.diamond.2015.03.008Get rights and content

Highlights

  • Original diamond coating process adapted to a wide variety of porous substrates

  • New self-supported diamond porous membranes with tunable pore size from few tens of micrometers to few tens of nanometers

  • Suitable devices for analytical chemistry: high flow filtration, separation/extraction and high surface area electrodes

  • Diamond membranes used for proteins extraction, recovery improvement through straightforward surface functionalization

Abstract

In this study, novel diamond porous membranes are developed through a reliable process providing a unique pathway toward large surface area and porous materials. Mainly deposited onto flat surface so far, we demonstrate here that diamond coating is possible on very complex 3D shapes, even nanoporous ones, through an original nanoseeding process and adapted growth conditions. Such membranes or filters exhibit outstanding features thanks to the unique mechanical properties and surface chemistry of diamond. Indeed, the straightforward tuning of their surface properties associated to their high stability ensures the diamond porous membranes' applications in the scope of filtration, separation and extraction. Preliminary electrochemical studies highlight the membranes' potential to be used for high specific area electrode applications. After an extensive characterization of these new diamond porous membranes, their potential for protein extraction will be demonstrated through mass spectrometry detection.

Introduction

Conventional analytical techniques require sample preparation steps [1] where several different approaches have been used to increase the specificity, the sensitivity and the accuracy of analytical detection tools. Among the current methods, solid phase extraction (SPE) [2], [3] stands out as the most suitable technique due to its low cost, its efficiency and its simplicity. SPE is mostly used for trace element detection [4] and analyte isolation in complex matrices [5]. Regarding industrial or large-scale applications, such as drug detection in biological fluids, pollutant trace detection and pharmaceutical and biological analyses, SPE remains the common technique used for sample preparation. One can note that the solid phase microextraction (SPME) approach is a faster and simplest derivative technique. Despite a lower retention potential when compared to conventional SPE, SPME is particularly well-adapted for field and on-site applications [6], [7], [8]. For an efficient SPE, the solid phase has to meet (i) a high surface area (ii) the best pore size homogeneity and (iii) an adapted surface chemistry. Up to now, silica solid phase remains the main material available on the marketplace due to its low cost and the large choice of bead size. However, the use of such silica phase involves complicated surface functionalization steps where glovebox conditions are often required. Indeed, although easier techniques such as silanization are available, the functionalized layers obtained are rather unstable thus not reliable.

In this context, we propose here a new approach where diamond can be used as an active solid phase material exhibiting very versatile and robust functionalization properties. Diamond exhibits many singular physical and chemical properties that drew the attention of numerous research groups with many and varied activities [9]. Its highest hardness associated to tremendous resilience gives diamond outstanding mechanical properties. Furthermore the high bonding energy of sp3 carbon bonds offers several unique features. For instance, diamond exhibits high working temperatures, total inertia toward ionization radiations and a chemical inertness. In terms of surface chemistry, diamond benefits from the usual carbon chemistry. Many functionalization routes are available not only in organic but also in aqueous phases. It provides access to the grafting of a wide range of cheap chemicals and so to numerous terminal moieties. Moreover, several functionalization ways lead to the formation of highly stable C–C covalent bonds. At last, diamond can be grown at a low cost to be either a highly insulating material or a conductive medium when doped with boron. Heavily boron doped diamond gives rise to an electrode material with a very large potential window in water and a low background current. The association of these two singular properties ensures diamond electrodes' unique perspectives in terms of detection, water treatment and depollution processes in water [10]. Besides its intrinsic antifouling capabilities [11], unusual defouling processes have also been made available [12], that allows a complete regeneration of the diamond electrode surfaces. This opens up the field for the detection of a large amount of species involving a fast, complete and irreversible fouling of usual electrodes through surface polymerization [16]. It also allows detection in media with high fouling capabilities, such as milk, blood and mud, without the need of electrode replacement or abrasion.

Following this unique combination of mechanical properties, chemical inertness and anti-fouling solutions, boron doped diamond porous membranes (BDD-PMs) appear as a very promising material for high flow microfiltration, and especially when made compatible with many industrial filtrations such as beverage and food processing and wastewater and water treatment. One can note that several studies have already highlighted the interest of diamond to be used as a platform for separation science [13], as a highly stable phase for SPE [14] and more generally as adsorbents for applications in chromatography [15]. Moreover, the variety, simplicity and stability of the grafting techniques onto diamond make BDD-PM a valuable candidate for solid phase extraction.

Surprisingly, there are very few studies available in the literature focusing on diamond material applications for SPE and they are all related to diamond nanoparticles [17], [18].

Conventional chemical vapor deposition (CVD) appears as one of the techniques available for diamond layer synthesis. To achieve porous materials, two approaches can be considered: (i) the first being based on etching processes [19], [20] and (ii) the second consisting in diamond coating of already porous substrates. This latter method has already been experienced in the literature, at least on carbon nanotubes [21], [22], and appeared to us as the most valuable technique. Here, we propose a coating method based on an optimized nano-seeding process via a layer by layer approach [23].

In this communication, we will detail how we have optimized this seeding approach to allow effective 3D diamond coating in order to fabricate a new type of boron doped diamond porous membrane (BDD-PM). The substrates used were low cost commercial fiberglass filters. A complete characterization that involves crystalline, chemical characterization as well as pore size assessment was carried out. A preliminary approach of the electrochemical assets of the membranes is introduced. Then, the BDD-PM extraction properties will be assessed through the filtration and extraction of the BSA followed by its detection with liquid chromatography tandem mass spectrometry (LC–MS/MS).

Section snippets

Chemicals

Lithium perchlorate, potassium ferricyanide, potassium ferrocyanide, phosphate buffered saline, sodium phosphate dibasic, and sodium hydroxide were purchased from Aldrich.

Seeding through Buchner filtration process

HPHT (high pressure high temperature) diamond nanoparticles (NDs) were purchased from Van Moppes (Syndia SYP 0-0.02). They exhibit an average size of 30 nm and a zeta potential value of around − 50 mV. Poly(diallyldimethylammonium chloride) (PDDAC, molecular weight 100,000–200,000) was purchased from Aldrich. 25 mm Whatman glass

Diamond membranes' development: seeding and growth

CVD diamond growth on non-diamond substrates has to be initiated by the presence of nuclei at the surface. On conductive and flat substrates, bias enhanced nucleation (BEN) can be efficiently applied to create in-situ nuclei. On non-conductive or 3D-shaped substrates, an alternative approach relies on the dispersion of diamond nanoparticles (NDs), so called the nanoseeding technique. Here, NDs will act as seeds for the CVD growth. Several nanoseeding techniques have been proposed in the

Conclusion

Heavily boron doped diamond porous membranes were fabricated using low cost commercial fiberglass filters. We optimized the synthesis process to ensure pore-size control in a highly reproducible manner. They benefit from the diamond surface properties, namely the versatile surface chemistry. Thanks to well-mastered functionalization routes, diamond porous membranes can exhibit tunable hydrophilic character or more advanced affinities. We have demonstrated that diamond membranes can be used as

Prime novelty statement

This work reports for the first time self-supporting diamond porous membranes suitable for analytical chemistry such as filtration, extraction and separation.

Acknowledgments

Sébastien Ruffinatto thankfully acknowledges the French CBRN program for supporting his grant.

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