Three Dimensional Carbon Nanosheets as a Novel Catalyst Support for Enzymatic Bioelectrodes

Umasankar, Yogeswaran; Brooks, Donald B.; Brown, Billyde; Zhou, Zhiguo; Ramasamy, Ramaraja P.

doi:10.1002/aenm.201301306

Cited by 31 publications

(27 citation statements)

References 39 publications

(86 reference statements)

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“…Carbon nanotubes (CNTs) have been intensively studied in the design of EFC electrodes . In particular, the emerging use of buckypaper (BP) electrodes has recently improved the processability and flexibility of CNT‐based electrodes in the design of flexible and wearable EFCs . BPs are commonly prepared from the filtration of a concentrated dispersion of surfactant‐wrapped CNTs using a nonionic surfactant bearing PEG groups such as Triton X‐100 .…”

Section: Introductionmentioning

confidence: 99%

A Diethyleneglycol‐Pyrene‐Modified Ru(II) Catalyst for the Design of Buckypaper Bioelectrodes and the Wiring of Glucose Dehydrogenases

et al. 2019

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A novel water-soluble Ru complex bearing phenanthrolinequinone ligands, diethyleneglycol linkers and pyrene anchoring groups was synthesized. Electrical wiring of NAD-and FADdehydrogenases is demonstrated via NADH oxidation and mediated electron transfer respectively. Bioelectrocatalysis is facilitated by the flexible and hydrophilic diethyleneglycol groups, and strong binding of pyrene groups with the carbon nanotubes (CNTs) of the electrodes. Furthermore, owing to the surfactant properties of the PEG-modified complex, high quality CNT dispersions were obtained for homogeneous buckypaper preparation.

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Section: Introductionmentioning

confidence: 99%

A Diethyleneglycol‐Pyrene‐Modified Ru(II) Catalyst for the Design of Buckypaper Bioelectrodes and the Wiring of Glucose Dehydrogenases

et al. 2019

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“…According to the attenuated total reflectance Fourier‐transform infrared spectroscopy (ATR‐FTIR) spectrum (Figure S7, Supporting Information), new peaks were observed at 1400, 1530, and 1640 nm after ClFDH immobilization. These peaks stemmed from hydrogen bonding vibration, NH bond bending vibration, and CO stretching vibration of amide bonds, respectively, owing to the ClFDH in the 3D TiN‐ClFDH cathode. Moreover, the EDS result in Figure S8 of the Supporting Information shows a uniform distribution of ClFDHs W atoms throughout the TiN nanoshell, demonstrating that ClFDHs were well‐distributed and not limited by the penetration depth.…”

Section: Resultsmentioning

confidence: 99%

Continuous 3D Titanium Nitride Nanoshell Structure for Solar‐Driven Unbiased Biocatalytic CO₂ Reduction

Kuk

Ham

Gopinath

et al. 2019

Advanced Energy Materials

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Z-scheme in natural photosynthesis are promising for solar-driven CO 2 conversion. [2] By combining multiple photoelectrodes or photovoltaics (PV), the Z-scheme PEC cells can provide sufficient photopotential to simultaneously drive water oxidation and CO 2 reduction under minimal or no external bias. [3] Nevertheless, lowering the kinetic barrier of thermodynamically inert CO 2 remains a hurdle for efficient CO 2 reduction. The development of CO 2reducing biocatalyst-conjugated cathodes can improve chemoselectivity and increase yield under mild conditions. [4] Compared to synthetic catalysts that often require extreme conditions such as high pressure, pH, or temperature, enzymes show high catalytic activities and specificities under mild conditions, making them a valuable catalyst for sustainable and green applications. In particular, formate dehydrogenase (FDH) is an attractive redox enzyme that reduces CO 2 to formate, an alternative water-soluble feedstock that can be easily converted to other common fuels. [5] Previous studies have focused on mediated electron transfer (MET)-type reactions, [6] in which redox mediators such as nicotinamide adenine dinucleotide cofactor (NADH) and Rh-based complexes shuttle electrons between an electrode and FDH. However, the MET-based biocatalysis requires costly electron mediators and multiple electron transfer steps that cause side reactions and significant losses in efficiency. [7] Here, we report the development of 3D titanium nitride nanoshell (3D TiN) electrodes for biocatalytic PEC cells that convert CO 2 to formate through direct electron transfer (DET), as depicted in Scheme 1a. A highly ordered, porous TiN structure is employed as an electrically conductive scaffold for efficient DET to a W-containing FDH from Clostridium ljungdahlii (ClFDH) (inset, Scheme 1a). TiN was chosen as a scaffold for DET-based bioelectrode because it is highly conductive, electrochemically stable and exhibit high chemical and thermal resistance, as well as exceptional hardness. [8] The 3D TiN electrode simultaneously provides (i) a large electroactive surface area generated from an ultrathin (≈30 nm), 3D nanoshell structure with high porosity (92.1%) for high enzyme loading per geometric area, (ii) a continuous electron transfer network with high electrical Z-scheme-inspired tandem photoelectrochemical (PEC) cells have received attention as a sustainable platform for solar-driven CO 2 reduction. Here, continuously 3D-structured, electrically conductive titanium nitride nanoshells (3D TiN) for biocatalytic CO 2 -to-formate conversion in a bias-free tandem PEC system are reported. The 3D TiN exhibits a periodically porous network with high porosity (92.1%) and conductivity (6.72 × 10 4 S m −1 ), which allows for high enzyme loading and direct electron transfer (DET) to the immobilized enzyme. It is found that the W-containing formate dehydrogenase from Clostridium ljungdahlii (ClFDH) on the 3D TiN nanoshell is electrically activated through DET for CO 2 reduction. At a low overpotential...

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“…Eq. 16 allows the determination of i 0 and b 568 . Further, the rate of electron transfer rate (k et ) can be obtained from:…”

Section: Approaches For the Improvement Of Efcs' Cell Voltagementioning

confidence: 99%

Tackling the Challenges of Enzymatic (Bio)Fuel Cells

et al. 2019

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The ever-increasing demands for clean and sustainable energy sources combined with rapid advances in bio-integrated portable or implantable electronic devices have stimulated intensive research activities in enzymatic (bio)fuel cells (EFCs). The use of renewable biocatalysts, the utilization of abundant green, safe, and high energy density fuels, together with the capability of working at modest and biocompatible conditions, make EFCs promising as next generation alternative power sources. However, the main challenges (low energy density, relatively low power density, poor operational stability and limited voltage output) hinder future applications of EFCs. This review aims at exploring the underlying mechanism of EFCs and providing possible practical strategies, methodologies and insights to tackle of these issues. Firstly, this review summarizes approaches in achieving high energy densities in EFCs, particularly, employing enzyme cascades for the deep/complete oxidation of fuels. Secondly, strategies for increasing power densities in EFCs, including increasing enzyme activities, facilitating electron transfers, employing nanomaterials, and designing more efficient enzyme-electrode interfaces, are described. The potential of EFCs/(super)capacitor combination is discussed. Thirdly, the review evaluates a range of strategies for improving the stability of EFCs, including the use of different enzyme immobilization approaches, tuning enzyme properties, designing protective matrixes, and using microbial surface displaying enzymes. Fourthly, approaches for the improvement of the cell voltage of EFCs are highlighted. Finally, future developments and a prospective on EFCs are envisioned.

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Three Dimensional Carbon Nanosheets as a Novel Catalyst Support for Enzymatic Bioelectrodes

Cited by 31 publications

References 39 publications

A Diethyleneglycol‐Pyrene‐Modified Ru(II) Catalyst for the Design of Buckypaper Bioelectrodes and the Wiring of Glucose Dehydrogenases

A Diethyleneglycol‐Pyrene‐Modified Ru(II) Catalyst for the Design of Buckypaper Bioelectrodes and the Wiring of Glucose Dehydrogenases

Continuous 3D Titanium Nitride Nanoshell Structure for Solar‐Driven Unbiased Biocatalytic CO₂ Reduction

Tackling the Challenges of Enzymatic (Bio)Fuel Cells

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Three Dimensional Carbon Nanosheets as a Novel Catalyst Support for Enzymatic Bioelectrodes

Cited by 31 publications

References 39 publications

A Diethyleneglycol‐Pyrene‐Modified Ru(II) Catalyst for the Design of Buckypaper Bioelectrodes and the Wiring of Glucose Dehydrogenases

A Diethyleneglycol‐Pyrene‐Modified Ru(II) Catalyst for the Design of Buckypaper Bioelectrodes and the Wiring of Glucose Dehydrogenases

Continuous 3D Titanium Nitride Nanoshell Structure for Solar‐Driven Unbiased Biocatalytic CO2 Reduction

Tackling the Challenges of Enzymatic (Bio)Fuel Cells

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Continuous 3D Titanium Nitride Nanoshell Structure for Solar‐Driven Unbiased Biocatalytic CO₂ Reduction