Laser-scribed Graphene Electrodes Research Articles

Activated and shorter Laser-Scribed graphene Electrodes: Excellent electrochemical signal amplification for detecting biomarkers

Laser-scribed graphene electrodes (LSGEs) are emerging as powerful transducers in electroanalysis. Surface structure and electrode geometry are the two key properties that heavily influence the characteristics of the resulting biosensors. In this work, we have investigated the sensing abilities of the LSGEs at various electrochemical activation procedures and electrode geometry conditions. We found that electrochemically activated LSGEs with shorter electrode connection lengths outperform corresponding non-activated LSGEs with longer electrode connection lengths. The effects of different pH conditions, supporting electrolytes, polarization potentials, and activation time were studied. X-ray photoelectron spectroscopy, Raman spectroscopy, and voltammetry techniques were used to examine the in-situ formation of porosity, introduction of surface oxygen functionalities, role of defect densities, and electrochemically accessible area. Dopamine is used as a model to study the sensing capabilities of the electrodes. Activated LSGE offered a 5.4-fold enhanced detection limit for dopamine compared to longer and non-activated LSGE. Practicality of the method is validated in human serum and urine samples. In addition, the sensor was demonstrated in monitoring in-situ dopamine released by neuroblastoma SH-SY5Y cells. Additionally, the enhanced sensing performance of the activated LSGEs are also tested by sensing uric acid and paracetamol. Electrochemically activated, shorter LSGEs hold great potential in various electrochemical applications.

Porous Laser-Scribed Graphene Electrodes Modified with Zwitterionic Moieties: A Strategy for Antibiofouling and Low-Impedance Interfaces.

Laser-scribed graphene electrodes (LSGEs) are promising platforms for the development of electrochemical biosensors for point-of-care settings and continuous monitoring and wearable applications. However, the frequent occurrence of biofouling drastically reduces the sensitivity and selectivity of these devices, hampering their sensing performance. Herein, we describe a versatile, low-impedance, and robust antibiofouling interface based on sulfobetaine-zwitterionic moieties. The interface induces the formation of a hydration layer and exerts electrostatic repulsion, protecting the electrode surface from the nonspecific adsorption of various biofouling agents. We demonstrate through electrochemical and microscopy techniques that the modified electrode exhibits outstanding antifouling properties, preserving more than 90% of the original signal after 24 h of exposure to bovine serum albumin protein, HeLa cells, and Escherichia coli bacteria. The promising performance of this antifouling strategy suggests that it is a viable option for prolonging the lifetime of LSGEs-based sensors when operating on complex biological systems.

Laser-scribing graphene-based electrochemical biosensing devices for simultaneous detection of multiple cancer biomarkers

In this study, a graphene electrochemical sensor based on laser graphene polymer material was proposed to induce graphene formation on polyimide substrates via fiber laser. The laser produces stable power and results to achieve the benefits of consistency, conductivity, and flexibility. The electrochemical three-electrodes were manufactured on polyimide to replace the traditional three-electrodes by achieving small size and portability. An electrode activation is the modification of laser-scribed graphene electrodes (LSG) to facilitate the binding of liver cancer sites. The evaluation is performed by differential pulse Voltammetry (DPV) to detect cancer proteins in the phosphate buffer saline (PBS) buffer and serum. In a serum environment, the concentrations of alpha-fetoprotein (AFP) and Carcinoembryonic antigen (CEA) were detected from 0.75 ng ml−1 to 100 ng ml−1, AFP and CEA electrodes have a good linear range (R2 = 0.96 and R2 = 0.98), indicating the sensor's sensitivity and specificity for cancer detection. In addition, two types of carcinogenic proteins were monitored in the PBS and successfully detected in this experiment. Based on the results, the appropriate LSG sensor may be used for monitoring with limited resources. Electrode manufacturing is simple, fast, low-cost, small in size, convenient to carry, stable, instant detection, and flexible.

Fabrication of flexible planar micro-supercapacitors using laser scribed graphene electrodes incorporated with MXene

The surge in demand for personalized electronic products has fueled the emergence and development of flexible electronic technology, giving rise to flexible energy storage devices. An integral component in these devices is planar micro-supercapacitors (MSCs), which hold immense promise for compatibility with flexible electronic products, especially in terms of their miniaturization, flexibility, integration, and customization. In this study, a fast, efficient, and environmentally friendly laser scribing technique has been employed to pattern MXene and graphene oxide (MXene/GO) composite films to prepare shape-controllable MXene and laser scribed graphene (MXene/LSG) patterned electrodes on a flexible substrate, which were then constructed into flexible MSCs. Based on the synergistic effect of these two-dimensional materials, MXene and LSG, the resulting adaptable devices exhibit exceptional electrochemical performance, including high areal capacitance, long cycle stability, superior flexibility, and mechanical stability. Furthermore, the use of a laser scribing process has pivotal implications for the scalable production of patterned electrodes and modular integration.

A Highly Sensitive Flexible Pressure Sensor Based on Inter-Comb Structured Graphene Electrodes

Susceptible and flexible pressure sensors have broad application prospects and market demands in bionic skin, human–machine interface, and intelligent wearable electronic devices. However, optimizing the sensor’s sensitivity through a simple, low-cost process is still a considerable challenge. In this work, the sensitivity of a capacitive pressure sensor was effectively improved by optimizing the geometry of the laser-scribed graphene (LSG) electrodes. The pressure sensor, based on the inter-comb structured LSG electrodes and polyvinyl pyrrolidone nanofiber membrane (PVP NM) dielectric layer, has a high sensitivity (4.352 kPa <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$^{-\text{1}}$</tex-math> </inline-formula> at 0–2 kPa), a fast response/recovery time (40/37 ms), an ultralow detection limit ( <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\sim$</tex-math> </inline-formula> 12 Pa), and excellent mechanical stability (6000 cycles). The sensor developed in this research can be used in health monitoring such as carotid artery pulsation and respiratory disease. In addition, the 6 <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\times$</tex-math> </inline-formula> 6 sensor array can precisely characterize the regional pressure distribution. This study demonstrates the significant potential of the inter-comb structured LSG electrodes in highly sensitive flexible pressure sensors.

Laser-scribed Graphene Electrodes Functionalized with Nafion/Fe3O4 Nanohybrids for the Ultrasensitive Detection of Neurotoxin Drug Clioquinol.

The analysis of pharmaceutical active ingredients plays an important role in quality control and clinical trials because they have a significant physiological effect on the human body even at low concentrations. Herein, a flexible three-electrode system using laser-scribed graphene (LSG) technology, which consists of Nafion/Fe3O4 nanohybrids immobilized on LSG as the working electrode and LSG counter and reference electrodes on a single polyimide film, is presented. A Nafion/Fe3O4/LSG electrode is constructed by drop coating a solution of Nafion/Fe3O4, which is electrostatically self-assembled between positively charged Fe3O4 and negatively charged Nafion on the LSG electrode and is used for the first time to determine a neurotoxicity drug (clioquinol; CQL) in biological samples. Owing to their porous 3D structure, an enriched surface area at the active edges and polar groups (OH, COOH, and −SO3H) in Nafion/Fe3O4/LSG electrodes resulted in excellent wettability to facilitate electrolyte diffusion, which gave ∼twofold enhancement in electrocatalytic activity over LSG electrodes. The experimental parameters affecting the analytical performance were investigated. The quantification of clioquinol on the Nafion/Fe3O4/LSG electrode surface was examined using differential pulse voltammetry and chronoamperometry techniques. The fabricated sensor displays preferable sensitivity (17.4 μA μM–1 cm–2), a wide linear range (1 nM to 100 μM), a very low detection limit (0.73 nM), and acceptable selectivity toward quantitative analysis of CQL. Furthermore, the reliability of the sensor was checked by CQL detection in spiked human blood serum and urine samples, and satisfactory recoveries were obtained.

A Portable Molecularly Imprinted Sensor for On-Site and Wireless Environmental Bisphenol A Monitoring.

The detection of pollutant traces in the public and environmental waters is essential for safety of the population. Bisphenol A (BPA) is a toxic chemical widely used for the production of food storage containers by plastic industries to increase the storage ability. However, the insertion of BPA in water medium leads to serious health risks. Therefore, the development of low-cost, practical, sensitive, and selective devices to monitor BPA levels on-site in the environment is highly needed. Herein, for the first time, we present a homemade portable potentiostat device integrated to a laser-scribed graphene (LSG) sensor for BPA detection as a practical environmental pollutant monitoring tool. Recently, there has been an increasing need regarding the development of graphene-based electrochemical transducers (e.g., electrodes) to obtain efficient biosensing platforms. LSG platform is combined with molecularly imprinted polymer (MIP) matrix. LSG electrodes were modified with gold nanostructures and PEDOT polymer electrodeposition to create a specific MIP biomimetic receptor for ultrasensitive BPA detection. The sensing device has a Bluetooth connection, wirelessly connected to a smartphone providing high sensitivity and sensitivity (LOD: 3.97 nM in a linear range of .01–10 µM) toward BPA. Two commercial bottled water samples, tap water, commercial milk, and baby formula samples have been used to validate the reliability of the portable sensor device.

Inherent Surface Activation of Laser-Scribed Graphene Decorated with Au and Ag Nanoparticles: Simultaneous Electrochemical Behavior toward Uric Acid and Dopamine.

Laser-scribed graphene electrodes (LSGEs) have attracted great attention for the development of electrochemical (bio)sensors due to their excellent electronic properties, large surface area, and high porosity, which enhances the electrons' transfer rate. An increasing active surface area and defect sites are the quickest way to amplify the electrochemical sensing attributes of the electrodes. Here, we have found that the activation procedure coupled to the electrodeposition of metal nanoparticles resulted in a significant amplification of the active area and the analytical performance. This preliminary study is supported by the demonstration of the simultaneous electrochemical sensing of dopamine (DA) and uric acid (UA) by the electrochemically activated LSGEs (LSGE*s). Furthermore, the electrodeposition of two different metal nanoparticles, gold (Au) and silver (Ag), was performed in multiple combinations on working and reference electrodes to investigate the enhancement in the electrochemical response of LSGE*s. Current enhancements of 32, 27, and 35% were observed from LSGE* with WE:Au/RE:LSG/CE:LSGE, WE:Au/RE:Au/CE:LSGE, and WE:Au/RE:Ag/CE:LSGE, compared to the same combinations of LSGEs without any surface activation. A homemade and practical potentiostat, KAUSTat, was used in these electrochemical depositions in this study. Among all of the combinations, the surface area was increased 1.6-, 2.0-, and 1.2-fold for WE:Au/RE:LSG/CE:LSGE, WE:Au/RE:Au/CE:LSGE, and WE:Au/RE:Ag/CE:LSGE prepared from LSGE*s, respectively. To evaluate the analytical performance, DA and UA were detected simultaneously in the presence of ascorbic acid. The LODs of DA and UA are calculated to be ∼0.8 and ∼0.6 μM, respectively. Hence, this study has the potential to open new insights into new surface activation strategies with a combination of one-step nanostructured metal depositions by a custom-made potentiostat. This novel strategy could be an excellent and straightforward method to enhance the electrochemical transducer sensitivity for various electrochemical sensing applications.

A novel electrochemical insulin aptasensor: From glassy carbon electrodes to disposable, single-use laser-scribed graphene electrodes

Insulin, a peptide hormone secreted by pancreatic β cells, affects the development of diabetes and associated complications. Herein, we propose an electrochemical aptasensor for sensitive and selective detection of insulin using laser-scribed graphene electrodes (LSGEs). Before using disposable LSGEs, the development and proof-of-concept sensing experiments were firstly carried out on research-grade glassy carbon electrode (GCE). The aptasensor is based on using Exonuclease I (Exo I) that catalyses the hydrolysis of single-stranded aptamers attached to the electrode surface; however, the hydrolysis does not occur if the insulin is bound to the aptamer. Therefore, the unbound aptamers are cleaved by Exo I while insulin-bound aptamers remain on the electrode surface. In the next step, the gold nanoparticle - aptamer (AuNPs-Apt) probes are introduced to the electrode surface to form a ‘sandwich’ structure with the insulin on the surface-attached aptamer. The redox probe, methylene blue (MB), intercalates into the aptamers' guanine bases and the sandwich structure of AuNPs-Apt/insulin/surface-bound aptamer amplifies electrochemical signal from MBs. The signal can be well-correlated to the concentrations of insulin. A limit of detection of 22.7 fM was found for the LSGE-based sensors and 9.8 fM for GCE-based sensors used for comparison and initial sensor development. The results demonstrate successful fabrication of the single-use and sensitive LSGEs-based sensors for insulin detection.

Paper-based optimized chemical fuel cell with laser-scribed graphene electrodes for energy harvesting

Paper-based optimized chemical fuel cell with laser-scribed graphene electrodes for energy harvesting

Laser-scribed graphene sensor based on gold nanostructures and molecularly imprinted polymers: Application for Her-2 cancer biomarker detection

Laser scribed graphene (LSG) has shown great potential as a sensing platform due to its high sensitivity, simplicity, porosity, and flexibility. In this context, we report a novel biosensing platform that utilizes LSG electrodes modified with nanostructured gold and molecularly imprinted polymer (MIP) to enhance its sensitivity and selectivity. This biomimetic sensing platform is used to detect the human epidermal growth factor receptor 2 (Her-2) protein, a significant breast cancer biomarker. Hence, a simple and accurate biomimetic sensor is developed in this study. To the best of our knowledge, this is the first report on nanostructured gold modified MIP-based LSG sensor for Her-2. LSG electrodes are fabricated by irradiation of a polyimide sheet using a CO2 laser. Nanostructured gold is electrodeposited onto the LSG to enhance its sensitivity and facilitate better Her-2 immobilization on the sensor surface. For MIP preparation, 3, 4-ethylenedioxythiophene (EDOT) was electropolymerized after pre-adsorption of Her-2 on the electrode surface for 20 min. The MIP deposition, removal, and adsorption parameters were investigated and optimized. The developed sensing strategy showed an excellent ability to detect Her-2 in the concentration range from 1 to 200 ng/mL with a LOD of 0.43 ng/mL. The biomimetic sensor showed high selectivity towards the detection of Her-2 in the presence of other interfering molecules and appreciable recovery values of Her-2 in the spiked undiluted human serum samples. Finally, to show the potential application of the developed LSG-AuNS-MIP sensor as a point-of-care device, the sensor is integrated with a homemade open-source electrochemical analyzer KAUSTat to detect Her-2.

Electrochemical aptasensor for 17β-estradiol using disposable laser scribed graphene electrodes

17β-Estradiol (E2), the strongest of the three major physiological estrogens in females, is an important factor in the female reproductive system. The abnormal level of E2 causes health issues, such as weak bones, urinary tract infections and even depression. Here, we present a novel, sensitive and selective, electrochemical aptasensor for detection of 17β-estradiol (E2). The E2 recognition aptamer was split into two fragments: the first fragment, functionalised with adamantane, is attached to poly(β-cyclodextrin) (poly(β-CD))-modified electrode surface through host-guest interactions between the adamantane and poly(β-CD). The second fragment, labelled with gold nanoparticles, forms the stem-loop structure with the first fragment only in the presence of E2. That specific recognition process triggers the change in the electrochemical signal (a change in the peak current from reduction of AuNPs), recorded by means of differential pulse voltammetry (DPV). The feasibility of the sensing design was firstly investigated on the commercially available glass carbon electrodes (GCE), with achieved a linear detection range of 1.0 × 10−13 to 1.0 × 10−8 M and a limit of detection (LoD) 0.7 fM. The sensing methodology was then translated onto single-use, disposable, laser-scribed graphene electrodes (LSGE) on a plastic substrate. The dynamic sensing range of E2 on LSGE was found to be 1.0 × 10−13 to 1.0 × 10−9 M, with a LoD of 63.1 fM, comparable to these of GCE. The successful translation of the developed E2 aptasensor from GCE to low-cost, disposable LSGE highlights a potential of this sensing platform in commercial, portable sensing detection systems for E2 and similar targets of biological interest.

Cover Picture: Laser‐scribed Graphene Electrodes as an Electrochemical Immunosensing Platform for Cancer Biomarker ‘eIF3d’ (Electroanalysis 4/2021)

The cover image is based on the Full Paper Laser-scribed Graphene Electrodes as an Electrochemical Immunosensing Platform for Cancer Biomarker ‘eIF3d' by Simge Balaban et al., DOI: 10.1002/elan.202060482.

Gold nanostructured laser-scribed graphene: A new electrochemical biosensing platform for potential point-of-care testing of disease biomarkers

Improvements in the laser-scribed graphene (LSG)-based electrodes are critical to overcoming limitations of bare LSG electrodes in terms of sensitivity, direct immobilization of detection probes for biosensor fabrication, and ease of integration with point-of-care (POC) devices. Herein, we introduce a new class of nanostructured gold modified LSG (LSG-AuNS) electrochemical sensing system comprising LSG-AuNS working electrode, LSG reference, and LSG counter electrode. LSG-AuNS electrodes are realized by electrodeposition of gold chloride (HAuCl4) solution, which gave~2-fold enhancement in sensitivity and electrocatalytic activity compared to bare LSG electrode and commercially available screen-printed gold electrode (SPAuE). We demonstrate LSG-AuNS electrochemical aptasensor for detecting human epidermal growth factor receptor 2 (Her-2) with a limit of detection (LOD) of 0.008 ng/mL and a linear range of 0.1–200 ng/mL. LSG-AuNS-aptasensor can easily detect different concentrations of Her-2 spiked in undiluted human serum. Finally, to show the LSG-AuNS sensor system's potential to develop POC biosensor devices, we integrated LSG-AuNS electrodes with a handheld electrochemical system operated using a custom-developed mobile application.

Laser scribed graphene: A novel platform for highly sensitive detection of electroactive biomolecules

Laser-scribed graphene electrodes (LSGEs) have recently shown a potential for the development of electrochemical biosensors thanks to their electronic properties, porous structures, and large surface area that can support the charge transfer. In this paper, the authors present a comparative study of the electrochemical performances of LSGEs with the conventional screen-printed carbon electrodes (SPCEs) toward the detection of most commonly used phenolic compounds and biomolecules. Cyclic voltammetry measurements showed a significant enhancement in the electron transfer rate of all tested electroactive species at LSGEs compared to conventional SPCE. We have suggested, for the first time, a mechanistic study for catecholamine redox reactions at LSGE as the electron transfer–chemical reaction–electron transfer mechanism. Moreover, the excellent performances of LSGE were observed in terms of the electrocatalytic detection of paracetamol (PCM). Therefore, the second part of this study compared the analytical performances of LSGE and SPCE with respect to the detection of PCM. The LSGE allows a fast and reversible system for PCM with a low ΔEp of 88 mV while the SPCE exhibits a quasi-reversible system with a higher ΔEp of 384 mV. The LSGE demonstrated a PCM linear range of concentration between 0.1 μM and 10 μM, with a detection limit of 31 nM. In addition, the LSGE showed a successful applicability with good selectivity and sensitivity for PCM determination in real samples of pharmaceutical tablets. Hence, LSGEs could be an excellent platform for simple and low-cost electrochemical biosensor applications.

Laser-scribed graphene (LSG) as new electrode material for impedance-based cellular assays

Impedance-based monitoring of cell-based assays has evolved to a multi-functional tool in fundamental and applied biomedical research. The majority of studies rely on gold-films as the electrode material which serves as growth surface and electrode at a time. Besides all its favorable properties like inertness, biocompatibility and superior electrochemical characteristics, gold-film electrodes in contact to cell culture medium show a capacitance of the electrode/electrolyte interface that may become limiting for the sensitivity of the readout. This study describes the use of laser-scribed graphene (LSG) as an alternative electrode material in impedance-based cell monitoring. LSG electrodes are prepared from commercial polyimide foils by simple CO2-laser-induced carbonization. The resulting electrodes show a 25times larger interface capacitance than standard gold-film electrodes due to their foam-like surface topography. Furthermore, LSG-electrodes are (i) highly compatible with cell attachment, (ii) easy to prepare in customized geometries from μm to cm with tunable surface topography and (iii) accessible by roll-to-roll production lines. We conclude from time- and frequency dependent impedance measurements of cell-covered LSG electrodes in direct comparison to the reference material gold that LSG provides an enormous potential to improve the sensitivity of impedance-based monitoring and electric-field mediated manipulation of adherent cells.

One-step electrosynthesized molecularly imprinted polymer on laser scribed graphene bisphenol a sensor

Bisphenol A (BPA) is a toxic chemical used by industries for production of containers for storage of food and beverages leading to possible health risks. In this work, we present a simple, mask-free, low-cost imprinted sensor based on laser scribed graphene (LSG) technology combined to molecularly imprinted polymers (MIPs) for BPA determination. CO2 laser was used in production of LSG electrodes with high conductivity and multilayer structure by using less laser speed/ power (2.8 cm/s /3.2 W) and low resistivity 58 Ω/square on flexible polyimide sheet leading to the high active surface area of the sensor. LSG device was functionalized with imprinted polypyrrole with a known amount of BPA as template molecule to develop the sensor. The bare LSG, LSG-MIP, LSG-NIP sensors were characterized using Raman spectroscopy, SEM, XRD, AFM. The electrochemical measurements were carried out using cyclic voltammetry and differential pulse voltammetry. Experimental conditions were optimized, including the concentration of pyrrole monomer, the number of polymerization cycles, the concentration of BPA as template and the incubation time. We evaluated the sensitivity of the LSG-MIP sensor in the concentration range between 0.05 μM and 20 μM with a limit of detection of 8 nM. The proposed sensor exhibits high selectivity towards BPA compared to its structural analogs and good reusability. The developed sensor was successfully applied for the detection of BPA in tap, mineral water and in plastic samples. The developed sensor was integrated into a PMMA case connected to the potentiostat to achieve complete isolation and a practical measurement system.

Laser-Scribed Graphene Electrodes Derived from Lignin for Biochemical Sensing

Laser scribing of porous graphene electrodes on flexible substrates is of great interest for developing disposable electrochemical biosensors. In this work, we present a new patterning process for highly conductive nitrogen-doped graphene derived from a lignin-based precursor. A CO2 laser scribing process was performed under ambient conditions to produce the porous graphene electrodes from lignin. The obtained nitrogen-doped laser-scribed graphene (N-LSG) is binder-free, hierarchical, and conductive. The interconnected carbon network displayed enhanced electrochemical activity with improved heterogeneous electron transfer rate. These features can be attributed to the high conductivity of porous N-LSG (down to 2.8 Ω per square) and its enriched active edge-plane sites. Furthermore, the N-LSG electrodes were decorated with MXene/Prussian blue (Ti3C2Tx/PB) composite via a simple spray-coating process, designed for sensitive detection of analytes. The Ti3C2Tx/PB-modified N-LSG electrodes were functionalized with catalytic enzymes for detecting glucose, lactate, and alcohol. The enzyme/Ti3C2Tx/PB/N-LSG electrodes exhibited remarkably enhanced electrochemical activity toward the detection of these biomarkers with a performance on par with previously reported on-chip carbon-based biosensors. Therefore, these materials have high potential for applications in personalized healthcare.

Enhancing the Efficiency of Graphene Oxide Reduction in Low-Power Digital Video Disc Drives by a Simple Precursor Heat Treatment.

Laser reduction of graphene oxide (GO) produces graphene effectively. As a low-power laser source, commercial digital video disc (DVD) drives provide a versatile platform to produce reduced graphene films in designed 2D patterns. However, research on how GO characteristics affect its laser reduction efficiency in DVD drives is rarely conducted. Here, we investigate how heating the GO dispersion affects the photoreduction process of GO films in a LightScribe DVD drive. Without noticeably changing the oxygen content, such mild heat treatment significantly improves GO's absorption in the visible region, resulting in significant enhancement on GO's laser reduction efficiency. We demonstrate that the laser reduction efficiency increases with the increasing treatment time. The enhanced reduction level greatly improves the performance of laser-scribed graphene electrodes in applications such as glucose sensors (with an optimal linear response range up to 2550 μM) and supercapacitors (with an optimal areal capacity of 1.37 mF cm-2 at the scan rate of 50 mV s-1). This proposed approach provides general insights into the production of laser-reduced graphene with low-power laser sources, for advanced device applications such as wearable electronics and flexible microelectronics.

Conductive Metal–Organic Frameworks Selectively Grown on Laser‐Scribed Graphene for Electrochemical Microsupercapacitors

AbstractConductive 2D metal–organic frameworks (MOFs) have merits beyond traditional MOFs for electrochemical applications, but reports on using MOFs as electrodes for electrochemical microsupercapacitors (MSCs) are practically non‐existent. In this work, a Ni‐catecholate‐based MOF (Ni‐CAT MOF) having good conductivity and exhibiting redox chemistry in the positive and negative voltage windows is developed. A novel process is developed to selectively grow the conductive Ni‐CAT MOF on 3D laser scribed graphene (LSG). The LSG with its superior wettability serves as a functional matrix‐current collector for the hybridization of conductive Ni‐CAT MOF nanocrystals. Impressively, MSCs fabricated using the hybrid LSG/Ni‐CAT MOF show significant improvement compared with MOF‐free LSG electrodes. Specifically, the LSG/Ni‐CAT MOF electrodes can deliver MSCs with a wide operating voltage (1.4 V), high areal capacitance (15.2 mF cm−2), energy density (4.1 µWh cm−2), power density (7 mW cm−2), good rate performance, and decent cycling stability. This work opens up an avenue for developing electrochemical microsupercapacitors using conductive MOF electrodes.