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Recent advances in high surface area electrodes for bioelectrochemical applications
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Current Opinion in
Electrochemistry
Review Article
Q1
Recent advances in high surface area electrodes for Q8 bioelectrochemical applications Q7
Nicolas Mano Abstract
The search for high surface area electrodes for bioelectrochemical applications is becoming more intense. In the last few years, new strategies have emerged to develop threedimensional electrode materials with very well controlled architecture providing at the same time high specific surface, bendability and flexibility. This review will highlight some of the recent work published in the last 2 years and will discuss the issue of mathematical modeling of porous electrodes and what could be the future of high surface area electrodes materials. Addresses CNRS, Centre de Recherche Paul Pascal (CRPP), UMR 5031, Univ. Bordeaux, 33600, Pessac, France Corresponding author: Mano, Nicolas ([email protected])
Current Opinion in Electrochemistry xxxx, xxx:xxx This review comes from a themed issue on Bioelectrochemistry Edited by Shelley Minter For a complete overview see the Issue and the Editorial Available online xxx https://doi.org/10.1016/j.coelec.2019.09.003 2451-9103/© 2019 Elsevier B.V. All rights reserved.
Keywords High surface area electrodes, Biosensors, Biofuel cells, Bioelectrochemical applications, Modeling.
Increasing electrodes active surface area has been one of the leading priority in bioelectrochemistry to increase enzyme loading and thus maximized current and/or power densities. From increasing the roughness of electrodes to using metallic structures or carbon-based materials in various forms (carbon nanotubes [CNT] [1,2], carbon black, carbon cryogels, graphene [3] .), 580 papers and many reviews dedicated to this topic have been published in the last ten years [4e17]. In the early work, various three-dimensional (3D) architectures have been proposed to increase the specific surface but without precise control of the orientation of those materials and regardless of the porosity and/or the electrode geometry. More recently, a more rational approach has been developed in the elaboration of electrodes material. Words such as hierarchical www.sciencedirect.com
porosities, defined and controlled architectures, flexibility, stretchable, bendable, or lightweight have emerged in the last 5 years. Intuitively, it can be easily understood that an ideal electrode material would be conductive and biocompatible ordered hierarchically 3D-structure combining mesopores (w2e50 nm diameter) to provide for enzyme immobilization and macropores (>500 m diameter) to allow for fast mass transport of substrates. But, this is a hard task to define the adequate pore size and the appropriate method of enzymes immobilization, as it depends on the nature of the enzyme, on the final applications and on other constraints such as diffusion of reactants for example [12]. Many interrelated parameters need to be taken into account which makes difficult to predict the adequate electrode design to maximize enzyme loading, electron transfer, and enzyme stability, to cite a few. Depending on the final applications, other considerations such as the weight, the flexibility, the cost, and the geometry/morphology of the final electrode should also be taken into account. For example, cylindrical geometry may be advantageous when substrates diffusion and concentration are small. Considering the recent excellent review published on electrode materials [9,12], in this short review, I will highlight the recent trend in the development of electrode materials in the last 2 years with a particular emphasis on the issue of modeling and on what could be the future of 3D electrodes for bioelectrochemical applications.
3d hierarchical porous electrodes The literature reports 3D metallic and nonmetallic porous electrodes with controlled pores size, thicknesses, and in some cases controlled distribution of the porosity. Among those materials, Tsujimura et al. [18] pioneered the use of magnesium oxide (MgOC) to elaborate meso/macroporous carbon electrode using 38 nm MgOC (Figure 1A). They later improved their method by combining two MgOC with sizes of 40 nm and 150 nm, showing the versatility of their approach [19]. The authors have studied in details the effect of the pore size and the ratio between the two MgOC on the efficiency of various enzymes, operating in direct electron transfer or mediated electron transfer (MET). From their work, they concluded that macropores Current Opinion in Electrochemistry xxxx, xxx:xxx
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Figure 1
improve the mass transfer of reactants, while mesopores allow for an efficient electron transfer. In 2018 [20], MgOC template carbon electrode made with 35 nm and 150 nm was used to immobilize a hydrogenase from Aquifex aeolicus. The authors demonstrated that pore size larger than the enzyme facilitates the enzyme loading and therefore the current, while pore size close to the enzyme hydrodynamic diameter promotes the stability. Using 3D metallic porous electrodes has been common in the last 2 years because they can be easily fabricated by many approaches [13,16]. For example, nanoporous gold electrodes with tunable pores diameters ranging from w20 nm to 500 nm are excellent platforms for enzymatic applications [21]. They can for example be made by sputtering, electrochemical dealloying (Figure 1b), or by anodization in glucose or oxalic solution [22,23] In addition, the pores can be further functionalized to provide for a better enzyme immobilization if needed. Kano et al. [24] used 3D porous gold electrodes prepared by anodization in oxalic acid or glucose solution to immobilize bilirubin oxidase (Figure 1c). Suitable pore size was achieved by tuning the glucose concentration during the anodization process and the surface area by modulating the anodization time. 0.5 M was found to be the optimum glucose concentration to generate mesopores allowing to enhance the curvature effects of the immobilized enzyme and thus the DET from the electrode to the enzyme. Unlike other approaches, Karajic et al. reported a bottom-up approach consisting in the electrodeposition of gold through a silica template, which after removal permits to obtain highly organized porous electrodes with controllable geometry, thickness, pore diameter, and pore distribution (Figure 1d) [25]. Zhang et al. [26] immobilized in such porous electrodes with 1200 nm diameter pores, an engineering bilirubin oxidase mutant and demonstrated that all the enzyme was immobilized within the porous structure. The authors noted that the current density was proportional to the electrode thickness. The two common denominators of these metallic and nonmetallic 3D hierarchical electrodes are the stabilizing effect of the enzyme upon immobilization and the mass transport limitation of substrates for high electrodes thicknesses.
(a) SEM images of the 38 nm MgOC-modified electrode fabricated by the electrophoretic deposition at 50 V over 1 min at 1000 × magnifications. Adapted with the permission of [18]. Copyright 2014 American Chemical Society. (b) SEM images of the electrochemically dealloyed polyethylene terephthalate/nanoporous gold electrode. Adapted with the permission of [34]. Copyright 2014 American Chemical Society. (c) SEM images of anodized Au electrode at 1.7 V in the presence of 0.1 M glucose in 0.1 M phosphate buffer (pH 7). Adapted with the permission of [57]. Copyright 2019 Elsevier. (d) SEM images of the outer surface of a macroporous electrode with crack free structure and homogeneous distribution of the pores. Adapted with the permission of [25]. Copyright 2019 Elsevier. SEM, scanning electron microscopy. Current Opinion in Electrochemistry xxxx, xxx:xxx
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Bioelectrochemical applications Mano
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Figure 2
Buckypaper-based biofuel cell. On the anodic side, buckypaper was functionalized with 1,10-phenanthroline-5,6-dione and FAD-dependent glucose dehydrogenase. On the cathodic side, buckypaper was modified with protoporphyrin and bilirubin oxidase. Reprint with permission from Ref. [30]. Copyright 2017, The American Chemical Society.
Flexible and stretchable electrodes With the expansion of wearable devices and paper-based electrodes [27e29], buckypapers (BPs) have emerged as a new class of high specific area materials, flexible and lightweight [30]. They are free-standing films made of entangled carbon nanotubes (CNTs) held by piepi stacking interactions, which can be further functionalized if needed [31]. BPs are light, flexible and bendable, to some degree, and are easily obtained for example by vacuum filtration of a CNTs solution. In 2017, Gross et al. [32] reported a high power BP glucose/O2 biofuel cell (Figure 2). Both anode and cathode were composed of self-standing BP made with non-functionalized multiwall CNTs. The system reached milliwatt per cube centimeter power densities. Sim et al. [33] recently designed a 380 mm diameter stretchable fibers biofuel cell by rewrapping multiwall CNTs sheets over the anodic and cathodic redox mediators and enzymes (Figure 3). The device could be stretched by 100% while yet producing a significant power density and exhibited enhance stability owing to the rewrapping structure. Other recent examples of stretchable/flexible devices include the development of a flexible lactate/O2 biofuel cell fabricated with nanoporous gold electrodes deposited onto polyterephtalate [34]. The device generated a maximum power density of 1.7 mW cm-2 in artificial tear containing 3 mM lactate. A carbon textile composite formed with 40 nm MgOC has been employed to elaborate the anode and cathode of an enzymatic biofuel cell, providing at the same time high flexibility and high specific surface [35].
simulations [37]. This is not the case in bioelectrochemistry. In the absence of enzymes, onedimensional empirical macroscopic models were introduced to model and simulate reversible and irreversible one electro processes at porous electrodes for both chronoamperometry and cyclic voltammetry [38,39]. But, those models did not provide any closure. To avoid this limitation and linked the pore-scale structure to the macroscale parameters, Le et al. [40,41] developed a multiscale model involving coupled reaction and diffusion using the volume averaging method. It permits to reduce the 3D problem to single spatial dimension with advantages in term of simulation time, simplicity and memory demand. Experimental data obtained for the reduction of O2 to hydrogen peroxide on porous gold electrodes of various thicknesses validated this model. In the presence of enzymes, whether operating in DET or MET, various analytical and numerical methods have been realized to decipher the mechanisms of immobilized enzymes on electrode surfaces [42e46], including biofuel cells [47]. But, most of these works have been restricted to nonporous electrodes. As in the case of nonmodified porous electrodes, modeling the behavior of porous enzymatic electrodes, in DET or MET, has simply been done empirically with 1 dimension macroscopic model [48e50]. Unsteady macroscopic models at the electrode scale, taking into account macroscopic and microscopic porosity, would be necessary to gain access to both enzymes and substrates concentration.
Concluding remarks Modeling Modeling the behavior of porous electrodes has been thoroughly documented for simulating batteries and fuel cells [36] and validated by 3D numerical www.sciencedirect.com
The quest for an ideal electrode material providing at the same time high surface area, fast mass transport of substrates, and efficient enzymes immobilization is still intense. The toolbox for creating 3D porous materials Current Opinion in Electrochemistry xxxx, xxx:xxx
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Figure 3
Fabrication and structure of biofuel cell fiber. (a) The fabrication process for stretchable biofuel cell fiber. For a stretchable biofuel cell fiber, the stretchable Q6 electrode was fabricated by MWNT sheet-wrapped rubber fiber. After the wrapping process, the stretchable electrode was coated with an active enzyme layer that is blended with an enzyme, redox mediator, and cross-linker. Finally, the active enzyme layer-coated electrode was rewrapped with MWNT sheets. The rewrapped structure was used to enhance electrode performance and stability of the biofuel cell fiber. (b) Schematic illustration of the structure and function of biofuel cell fiber. The anode enzyme and redox mediator polymer used were glucose oxidase (GOx) and mediator I, respectively. The cathode enzyme and redox mediator polymer used were bilirubin oxidase (BOx) and mediator II, respectively. Reprint with permission from Ref. [33]. Copyright 2018, The American Chemical Society.
with defined thicknesses and porosities distribution, or not, exists. 3D printing may also bring interesting opportunities in the near future to elaborate such sophisticated materials [51]. Up to now, most of the porous electrodes have consistently been designed empirically and many questions stay open. For example, questions on the chemical nature of the pore and its diameter and how it should be optimally designed remain unknown. To answer those questions, 3D materials may be elaborated with a rational approach. Mathematical models capable of predicting the optimal thickness, porosity, and mass transport limitation may be an essential tool for a rational optimization and improvement of porous electrodes for bioelectrochemical applications. The pore size, their chemical nature, and the thickness of the final porous electrode should be tuned in function of the enzyme and its application. The challenge will consist of being able to take into account numerous parameters including electron transfer between enzymes and electrodes surface, diffusion of substrates and products, with limited unknown variables. In relation with modeling, focused ion beam/scanning electron microscopy [52] or the use of X-rays computed tomography [53] may help in getting real images of the Current Opinion in Electrochemistry xxxx, xxx:xxx
structure of the materials and gain more insight into the void/pores distribution. Such images would be of great importance to refine mathematical models, specifically with hierarchical porosities or gradients of pores. Another open question is whether all the pores are modified by the enzymes and homogeneously distributed or not within all the porosity. Such information would be crucial to fuel mathematical models and relate enzymes conformation with kinetics. Do et al. reported earlier that the thicker the porous material, the more difficult was the penetration of the enzyme during the coating process deeper in the pores far from the free surface of the electrode [50]. It would, therefore, make no sense to elaborate very thick porous electrodes with the aim to maximize the specific surface if the entire surface of the electrode is not used for the catalysis. Particularly, if unmodified parts of the electrodes are subject to parasitic reactions. In addition, mass transport limitations may exist for thick electrodes. Confocal fluorescence with labeled enzymes may provide such information and has for example been reported for bilirubin oxidases within CNTs fibers and porous gold electrodes [26,54]. If such analytical technique can prove that a porous electrode is fully or partially www.sciencedirect.com
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modified with enzymes, the resolution is not high enough to distinguish between homogeneous and not homogeneous distribution. Being able to image enzymes within the porosity at the nanometer resolution would be a tremendous technical and experimental challenge. Finally, the growing number of porous electrodes, different in size, porosity, geometry, weight .. raises the question of the normalization of the results. This point has already been discussed on numerous occasions but nothing has yet been definitely implemented by the community [13,16,55,56].
Conflict of interest The author does not report any conflict of interest.
Acknowledgements The author thanks the financial support from the ANR (ANR-16-CE190001-03 and ANR-17-CE08-0005) and from the LabEx AMADEus (ANR10-LABX-42) within IdEx Bordeaux (ANR-10-IDEX-03-02), i.e. the “Investissements d’Avenir Programme” of the French government Q4 managed by the Agence Nationale de la Recherche (ANR).
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Available online at www.sciencedirect.com
ScienceDirect
Current Opinion in
Electrochemistry
Review Article
Q1
Recent advances in high surface area electrodes for Q8 bioelectrochemical applications Q7
Nicolas Mano Abstract
The search for high surface area electrodes for bioelectrochemical applications is becoming more intense. In the last few years, new strategies have emerged to develop threedimensional electrode materials with very well controlled architecture providing at the same time high specific surface, bendability and flexibility. This review will highlight some of the recent work published in the last 2 years and will discuss the issue of mathematical modeling of porous electrodes and what could be the future of high surface area electrodes materials. Addresses CNRS, Centre de Recherche Paul Pascal (CRPP), UMR 5031, Univ. Bordeaux, 33600, Pessac, France Corresponding author: Mano, Nicolas ([email protected])
Current Opinion in Electrochemistry xxxx, xxx:xxx This review comes from a themed issue on Bioelectrochemistry Edited by Shelley Minter For a complete overview see the Issue and the Editorial Available online xxx https://doi.org/10.1016/j.coelec.2019.09.003 2451-9103/© 2019 Elsevier B.V. All rights reserved.
Keywords High surface area electrodes, Biosensors, Biofuel cells, Bioelectrochemical applications, Modeling.
Increasing electrodes active surface area has been one of the leading priority in bioelectrochemistry to increase enzyme loading and thus maximized current and/or power densities. From increasing the roughness of electrodes to using metallic structures or carbon-based materials in various forms (carbon nanotubes [CNT] [1,2], carbon black, carbon cryogels, graphene [3] .), 580 papers and many reviews dedicated to this topic have been published in the last ten years [4e17]. In the early work, various three-dimensional (3D) architectures have been proposed to increase the specific surface but without precise control of the orientation of those materials and regardless of the porosity and/or the electrode geometry. More recently, a more rational approach has been developed in the elaboration of electrodes material. Words such as hierarchical www.sciencedirect.com
porosities, defined and controlled architectures, flexibility, stretchable, bendable, or lightweight have emerged in the last 5 years. Intuitively, it can be easily understood that an ideal electrode material would be conductive and biocompatible ordered hierarchically 3D-structure combining mesopores (w2e50 nm diameter) to provide for enzyme immobilization and macropores (>500 m diameter) to allow for fast mass transport of substrates. But, this is a hard task to define the adequate pore size and the appropriate method of enzymes immobilization, as it depends on the nature of the enzyme, on the final applications and on other constraints such as diffusion of reactants for example [12]. Many interrelated parameters need to be taken into account which makes difficult to predict the adequate electrode design to maximize enzyme loading, electron transfer, and enzyme stability, to cite a few. Depending on the final applications, other considerations such as the weight, the flexibility, the cost, and the geometry/morphology of the final electrode should also be taken into account. For example, cylindrical geometry may be advantageous when substrates diffusion and concentration are small. Considering the recent excellent review published on electrode materials [9,12], in this short review, I will highlight the recent trend in the development of electrode materials in the last 2 years with a particular emphasis on the issue of modeling and on what could be the future of 3D electrodes for bioelectrochemical applications.
3d hierarchical porous electrodes The literature reports 3D metallic and nonmetallic porous electrodes with controlled pores size, thicknesses, and in some cases controlled distribution of the porosity. Among those materials, Tsujimura et al. [18] pioneered the use of magnesium oxide (MgOC) to elaborate meso/macroporous carbon electrode using 38 nm MgOC (Figure 1A). They later improved their method by combining two MgOC with sizes of 40 nm and 150 nm, showing the versatility of their approach [19]. The authors have studied in details the effect of the pore size and the ratio between the two MgOC on the efficiency of various enzymes, operating in direct electron transfer or mediated electron transfer (MET). From their work, they concluded that macropores Current Opinion in Electrochemistry xxxx, xxx:xxx
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Figure 1
improve the mass transfer of reactants, while mesopores allow for an efficient electron transfer. In 2018 [20], MgOC template carbon electrode made with 35 nm and 150 nm was used to immobilize a hydrogenase from Aquifex aeolicus. The authors demonstrated that pore size larger than the enzyme facilitates the enzyme loading and therefore the current, while pore size close to the enzyme hydrodynamic diameter promotes the stability. Using 3D metallic porous electrodes has been common in the last 2 years because they can be easily fabricated by many approaches [13,16]. For example, nanoporous gold electrodes with tunable pores diameters ranging from w20 nm to 500 nm are excellent platforms for enzymatic applications [21]. They can for example be made by sputtering, electrochemical dealloying (Figure 1b), or by anodization in glucose or oxalic solution [22,23] In addition, the pores can be further functionalized to provide for a better enzyme immobilization if needed. Kano et al. [24] used 3D porous gold electrodes prepared by anodization in oxalic acid or glucose solution to immobilize bilirubin oxidase (Figure 1c). Suitable pore size was achieved by tuning the glucose concentration during the anodization process and the surface area by modulating the anodization time. 0.5 M was found to be the optimum glucose concentration to generate mesopores allowing to enhance the curvature effects of the immobilized enzyme and thus the DET from the electrode to the enzyme. Unlike other approaches, Karajic et al. reported a bottom-up approach consisting in the electrodeposition of gold through a silica template, which after removal permits to obtain highly organized porous electrodes with controllable geometry, thickness, pore diameter, and pore distribution (Figure 1d) [25]. Zhang et al. [26] immobilized in such porous electrodes with 1200 nm diameter pores, an engineering bilirubin oxidase mutant and demonstrated that all the enzyme was immobilized within the porous structure. The authors noted that the current density was proportional to the electrode thickness. The two common denominators of these metallic and nonmetallic 3D hierarchical electrodes are the stabilizing effect of the enzyme upon immobilization and the mass transport limitation of substrates for high electrodes thicknesses.
(a) SEM images of the 38 nm MgOC-modified electrode fabricated by the electrophoretic deposition at 50 V over 1 min at 1000 × magnifications. Adapted with the permission of [18]. Copyright 2014 American Chemical Society. (b) SEM images of the electrochemically dealloyed polyethylene terephthalate/nanoporous gold electrode. Adapted with the permission of [34]. Copyright 2014 American Chemical Society. (c) SEM images of anodized Au electrode at 1.7 V in the presence of 0.1 M glucose in 0.1 M phosphate buffer (pH 7). Adapted with the permission of [57]. Copyright 2019 Elsevier. (d) SEM images of the outer surface of a macroporous electrode with crack free structure and homogeneous distribution of the pores. Adapted with the permission of [25]. Copyright 2019 Elsevier. SEM, scanning electron microscopy. Current Opinion in Electrochemistry xxxx, xxx:xxx
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Figure 2
Buckypaper-based biofuel cell. On the anodic side, buckypaper was functionalized with 1,10-phenanthroline-5,6-dione and FAD-dependent glucose dehydrogenase. On the cathodic side, buckypaper was modified with protoporphyrin and bilirubin oxidase. Reprint with permission from Ref. [30]. Copyright 2017, The American Chemical Society.
Flexible and stretchable electrodes With the expansion of wearable devices and paper-based electrodes [27e29], buckypapers (BPs) have emerged as a new class of high specific area materials, flexible and lightweight [30]. They are free-standing films made of entangled carbon nanotubes (CNTs) held by piepi stacking interactions, which can be further functionalized if needed [31]. BPs are light, flexible and bendable, to some degree, and are easily obtained for example by vacuum filtration of a CNTs solution. In 2017, Gross et al. [32] reported a high power BP glucose/O2 biofuel cell (Figure 2). Both anode and cathode were composed of self-standing BP made with non-functionalized multiwall CNTs. The system reached milliwatt per cube centimeter power densities. Sim et al. [33] recently designed a 380 mm diameter stretchable fibers biofuel cell by rewrapping multiwall CNTs sheets over the anodic and cathodic redox mediators and enzymes (Figure 3). The device could be stretched by 100% while yet producing a significant power density and exhibited enhance stability owing to the rewrapping structure. Other recent examples of stretchable/flexible devices include the development of a flexible lactate/O2 biofuel cell fabricated with nanoporous gold electrodes deposited onto polyterephtalate [34]. The device generated a maximum power density of 1.7 mW cm-2 in artificial tear containing 3 mM lactate. A carbon textile composite formed with 40 nm MgOC has been employed to elaborate the anode and cathode of an enzymatic biofuel cell, providing at the same time high flexibility and high specific surface [35].
simulations [37]. This is not the case in bioelectrochemistry. In the absence of enzymes, onedimensional empirical macroscopic models were introduced to model and simulate reversible and irreversible one electro processes at porous electrodes for both chronoamperometry and cyclic voltammetry [38,39]. But, those models did not provide any closure. To avoid this limitation and linked the pore-scale structure to the macroscale parameters, Le et al. [40,41] developed a multiscale model involving coupled reaction and diffusion using the volume averaging method. It permits to reduce the 3D problem to single spatial dimension with advantages in term of simulation time, simplicity and memory demand. Experimental data obtained for the reduction of O2 to hydrogen peroxide on porous gold electrodes of various thicknesses validated this model. In the presence of enzymes, whether operating in DET or MET, various analytical and numerical methods have been realized to decipher the mechanisms of immobilized enzymes on electrode surfaces [42e46], including biofuel cells [47]. But, most of these works have been restricted to nonporous electrodes. As in the case of nonmodified porous electrodes, modeling the behavior of porous enzymatic electrodes, in DET or MET, has simply been done empirically with 1 dimension macroscopic model [48e50]. Unsteady macroscopic models at the electrode scale, taking into account macroscopic and microscopic porosity, would be necessary to gain access to both enzymes and substrates concentration.
Concluding remarks Modeling Modeling the behavior of porous electrodes has been thoroughly documented for simulating batteries and fuel cells [36] and validated by 3D numerical www.sciencedirect.com
The quest for an ideal electrode material providing at the same time high surface area, fast mass transport of substrates, and efficient enzymes immobilization is still intense. The toolbox for creating 3D porous materials Current Opinion in Electrochemistry xxxx, xxx:xxx
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Figure 3
Fabrication and structure of biofuel cell fiber. (a) The fabrication process for stretchable biofuel cell fiber. For a stretchable biofuel cell fiber, the stretchable Q6 electrode was fabricated by MWNT sheet-wrapped rubber fiber. After the wrapping process, the stretchable electrode was coated with an active enzyme layer that is blended with an enzyme, redox mediator, and cross-linker. Finally, the active enzyme layer-coated electrode was rewrapped with MWNT sheets. The rewrapped structure was used to enhance electrode performance and stability of the biofuel cell fiber. (b) Schematic illustration of the structure and function of biofuel cell fiber. The anode enzyme and redox mediator polymer used were glucose oxidase (GOx) and mediator I, respectively. The cathode enzyme and redox mediator polymer used were bilirubin oxidase (BOx) and mediator II, respectively. Reprint with permission from Ref. [33]. Copyright 2018, The American Chemical Society.
with defined thicknesses and porosities distribution, or not, exists. 3D printing may also bring interesting opportunities in the near future to elaborate such sophisticated materials [51]. Up to now, most of the porous electrodes have consistently been designed empirically and many questions stay open. For example, questions on the chemical nature of the pore and its diameter and how it should be optimally designed remain unknown. To answer those questions, 3D materials may be elaborated with a rational approach. Mathematical models capable of predicting the optimal thickness, porosity, and mass transport limitation may be an essential tool for a rational optimization and improvement of porous electrodes for bioelectrochemical applications. The pore size, their chemical nature, and the thickness of the final porous electrode should be tuned in function of the enzyme and its application. The challenge will consist of being able to take into account numerous parameters including electron transfer between enzymes and electrodes surface, diffusion of substrates and products, with limited unknown variables. In relation with modeling, focused ion beam/scanning electron microscopy [52] or the use of X-rays computed tomography [53] may help in getting real images of the Current Opinion in Electrochemistry xxxx, xxx:xxx
structure of the materials and gain more insight into the void/pores distribution. Such images would be of great importance to refine mathematical models, specifically with hierarchical porosities or gradients of pores. Another open question is whether all the pores are modified by the enzymes and homogeneously distributed or not within all the porosity. Such information would be crucial to fuel mathematical models and relate enzymes conformation with kinetics. Do et al. reported earlier that the thicker the porous material, the more difficult was the penetration of the enzyme during the coating process deeper in the pores far from the free surface of the electrode [50]. It would, therefore, make no sense to elaborate very thick porous electrodes with the aim to maximize the specific surface if the entire surface of the electrode is not used for the catalysis. Particularly, if unmodified parts of the electrodes are subject to parasitic reactions. In addition, mass transport limitations may exist for thick electrodes. Confocal fluorescence with labeled enzymes may provide such information and has for example been reported for bilirubin oxidases within CNTs fibers and porous gold electrodes [26,54]. If such analytical technique can prove that a porous electrode is fully or partially www.sciencedirect.com
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modified with enzymes, the resolution is not high enough to distinguish between homogeneous and not homogeneous distribution. Being able to image enzymes within the porosity at the nanometer resolution would be a tremendous technical and experimental challenge. Finally, the growing number of porous electrodes, different in size, porosity, geometry, weight .. raises the question of the normalization of the results. This point has already been discussed on numerous occasions but nothing has yet been definitely implemented by the community [13,16,55,56].
Conflict of interest The author does not report any conflict of interest.
Acknowledgements The author thanks the financial support from the ANR (ANR-16-CE190001-03 and ANR-17-CE08-0005) and from the LabEx AMADEus (ANR10-LABX-42) within IdEx Bordeaux (ANR-10-IDEX-03-02), i.e. the “Investissements d’Avenir Programme” of the French government Q4 managed by the Agence Nationale de la Recherche (ANR).
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