Graphene-based Catalysts Research Articles

Machine learning assisted screening of nitrogen-doped graphene-based dual-atom hydrogen evolution electrocatalysts

Nitrogen doped graphene-based dual-atom catalysts (NG-DACs) usually exhibit high reactivity for hydrogen evolution reaction (HER). The experimental design of efficient DACs-based HER catalysts, however, is time-consuming and expensive. In this work, a density functional theory combined with machine learning (DFT-ML) strategy is adopted towards the rapid screening of NG-DACs HER catalyst. The adsorption energies of HER intermediates on NG-DACs obtained by DFT calculations and their elemental features were used for the ML database construction. The prediction performance of three ML algorithms was evaluated, and gradient boosted regression (GBR) is found exhibit the best prediction accuracy. Using the HER energetics on Pt (111) as reference, quick screening of the NG-DACs with high HER activity was achieved, resulting to twenty-four potential catalysts. Further selection and validation of the ML-screened catalysts were performed by the hydrogen adsorption Gibbs free energy analysis. Accordingly, four promising NG-DACs HER catalysts were predicted using the proposed DFT-ML based catalyst prediction framework. The DFT-ML strategy offers an promising approach for the screening of new HER electrocatalysts.

Graphene-Based Catalysts: Emerging Applications and Potential Impact.

Carbon nanofillers in general and graphene in particular are considered as promising potential candidates in catalysis due to their two-dimensional (2D) nature, zero bandwidth, single atom thickness with a promising high surface area: volume ratio. Additionally, graphene oxide via result of tunable electrical properties has also been developed as a catalytic support for metal and metal oxide nanofillers. Moreover, the possession of higher chemical stability followed by ultrahigh thermal conductivity plays a prominent role in promoting higher reinforcement of catalytically active sites. In this review we have started with an overview of carbon nanofillers as catalyst support, their main characteristics and applications for their use in heterogeneous catalysis. The review article also critically focusses on the catalytic properties originating from both functional groups as well as doping. An in-depth literature on the various reaction catalysed by metal oxide based nanoparticles supported on GO/rGO has also been incorporated with a special focus on the overall catalytic efficiency with respect to graphene contribution. The future research prospective in the aforementioned field has also been discussed.

Control of burning rate pressure sensitivity for solid propellants by changing the interfacial contact of Al/HMX/AP with precisely located graphene-based energetic catalysts

The control of burning rate pressure sensitivity is essential for stable and reliable combustion of solid propellants. It has been proved that the combustion behavior of propellants can be effectively tuned by interfacial control of Al/oxidizers. In this work, core-shell Al-based composites, using oxidizers such as ammonium perchlorate (AP) and cyclotetramethylene tetranitramine (HMX) as the shell layer, have been prepared with a well-controlled location of graphene-based carbohydrazide complexes (GO-CHZ-M, M = Co2+ or Ni2+) as the catalysts. The catalysts can be located inside HMX or embedded on the surface of AP particles. The decomposition of AP and HMX could be greatly promoted with a trace amount of catalyst. Under the synergistic effects of Al/oxidizer interfacial control and GO-CHZ-M, the ignition delay time is shortened by >48 % with increased in flame radiation. More importantly, the burning rate (r) and pressure exponent (n) of the solid propellants are effectively regulated in a wide range. In particular, the use of Al@HMX/Co results in a lowered n of 0.29 within 1∼20 MPa compared to 0.79 for the blank reference sample. The agglomeration of Al particles during combustion was also inhibited due to the micro-explosion effect of Al@HMX composites. Novelty and Significance statementThe innovative approaches of integrating Al/HMX/AP composites and precise catalysis of graphene-based energetic catalysts in solid propellants have successfully achieved, regarding the modulation of the burning rates and pressure sensitivity. Moreover, the effect of catalyst location on the ignition delay and burning rates has also been studied thoroughly and clarified. This paper provides new insight into the regulation of combustion performance of solid propellants, with improved reaction efficiency and maintained energy density.

Evolution of Oxygen Content of Graphene Oxide for Humidity Sensing.

Graphene oxide (GO) has shown significant potential in humidity sensing. It is well accepted that the oxygen-containing functional groups in GO significantly influence its humidity sensing performance. However, the relationship between the content of these groups and the humidity sensing capability of GO-based sensors remains unclear. In the present work, we investigate the role of oxygen-containing functional groups in the humidity sensing performance by oxidizing graphite with mesh numbers 80-120, 325, and 8000 using the Hummers method, resulting in GO-80, GO-325, and GO-8000. Infrared spectroscopy (IR) and X-ray photoelectron spectroscopy (XPS) were used to identify the types and quantification of oxygen-containing functional groups. Molecular dynamics simulation is used to simulate the adsorption energy, intercalation dynamics, and hydrogen bonding of water molecules. Electrochemical tests were used to compare the adsorption/desorption time and response sensitivity of graphene oxide to humidity. It is proposed that hydroxyl and carboxyl groups are the main contributing groups to humidity sensing. GO-8000 shows a relatively fast response time, but the large number of carboxyl groups will hinder intercalation of water molecules, thus exhibiting lower sensitivity. This research provides a reference for the future development of graphene-based sensors, catalysts, and environmental materials.

Activity evaluation and reaction mechanisms of highly efficient dual-atom transition metal catalysts in Li-CO2 batteries

Lithium-carbon dioxide (Li-CO2) batteries have received increased attention due to their high energy density and fixing CO2 as a major greenhouse gas. At the same time, there are challenges including low activity of cathode and high overpotential in Li-CO2 batteries. Herein, 45 dual-atom catalysts (DACs) composed of 9 transition metal (TM) atoms doped in nitrogen-doped graphene (M1M2-N-G, M1, M2 = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn), as cathode catalysts of Li-CO2 batteries, have been studied by using first-principles calculations. According to the thermodynamic stability of the DACs and the ability of CO2 activation, 25 catalysts candidates were screened out. Then, the reaction activity and selectivity of DACs were evaluated by thermodynamical reaction energy and overpotential. Finally, TiMn-N-G displayed the smallest total electrode overpotential 1.83 V during the pathway of Li2CO3 and CrNi-N-G exhibited the smallest total electrode overpotential 0.08 V during the in Li2C2O4 pathway, respectively, which proved that they possessed better catalytic activity tendency in Li-CO2 batteries. This work provides not only a rational design to identify promising graphene-based catalysts, but also a general screen rule for atomic catalysts in Li-CO2 batteries.

Preparation and Decomposition of Spherical CL-20 Composites with Enhanced Laser Absorbance and Decreased Mechanical Sensitivity.

Direct initiation of secondary explosives by a semiconductor laser is highly demanded, but it is challenging to exclude the use of sensitive primers. Most laser-sensitive energetic materials are usually mechanically sensitive. In order to reduce the mechanical sensitivity (MS) of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) while improving laser absorbance in the near-infrared band, spherical CL-20 composites (SCCs) embedded with nano aluminum (Al) powder and graphene-based catalyst (GO-CHZ-Co) were prepared by a spray drying method. These SCCs have been characterized comprehensively in terms of their morphologies, particle size distribution, laser absorbance, thermal decomposition behaviors, MS, and laser ignition properties. Results show that the maximum critical impact energy of SCCs was 3.8 J, which is 2.8 J higher than that of pristine ε-CL-20. The critical friction load was increased by at most 108 N compared to pristine CL-20. The absorbance has also been significantly increased up to almost 70% in the wavelength between 400 and 1400 nm, where the peak absorption is located in the region of 800-900 nm. In addition, the initial decomposition temperature (Ti) of SCCs is lower than that of pure CL-20, especially in the presence of GO-CHZ-Co. The apparent activation energy (Ea) for the decomposition of SCCs was largely dependent on the particle size of Al. Preliminary ignition tests indicate that the SCCs can be ignited successfully by a small-power laser.

Nitrogen reduction reaction enhanced by single-atom transition metal catalysts on functionalized graphene: A first-principles study

Ammonia production seeks alternatives to the conventional Haber-Bosch process, with nitrogen reduction reaction (NRR) emerging promising. Addressing the challenge of efficient catalysts, the functionalized graphene-based single atom catalysts (SACs) stand out. While prior studies have favored heteroatom-doped catalysts, the coordination of metal centers with nitrogen atoms remains underexplored. This work investigates transition metal (TM) SACs on nitrogen-doped graphene (N3G) using density functional theory (DFT) for electro-catalytic NRR. Results highlight the stability of V@N3G, Mo@N3G, W@N3G, with binding energies of −7.77, −5.43, and −3.89 eV, respectively. Insights into work function, d-band center, N–N bond, and IR stretching's role in N2 activation are gained through this study. Bader charge analysis reveals electron redistribution between the support and adsorbed N2. Employing Computational Hydrogen Electrode (CHE) method, comparative free energy diagrams for TM@N3G (V, Mo, W) via., enzymatic, consecutive, alternating, and distal pathways outline potential rate determining step (PDS) with and without the Implicit solvation method. Remarkably, W@N3G catalyst exhibits the lowest PDS in the presence of solvation energy, surpassing other catalysts. The multi-adsorption of N2 on W@N3G enhances NRR process, stabilizing intermediates for efficient ammonia production. This computational study sheds light on metal center SACs on functionalized graphene support as a potential electro-catalyst for efficient and stable NRR.

Iron-based graphene composite for oxygen reduction reaction in alkaline media: Electrocatalytic activity and lifetime evaluation

The development of electrocatalysts with high catalytic performance and low costs for oxygen reduction reaction (ORR) is still challenging. Herein, an overall solution for ORR in alkaline media, from the catalyst synthesis to catalyst regeneration and to the development of a rapid, reliable and easy approach for electrode surface evaluation, is presented. We focused on the development and characterization of an efficient material for ORR in alkaline media, α-Fe2O3 N-doped graphene (Fe-N-Gr). The associative pathway for the four electron transfer ORR mechanism is sustained by the Raman spectra recorded from the electrode surface. We highlighted the possibility of catalyst regeneration by a simple electrochemical method. After two regeneration rounds and 1500 cycles in O2-saturated 1 M NaOH, the catalyst still retains 40.8 % catalytic activity. Finally, as a part of the overall solution, we demonstrated that a methodology based on Raman spectroscopic measurements and machine learning algorithms can be applied for graphene-based catalysts lifetime investigation.

Kinetics and thermodynamics in microwave-assisted transesterification of palm oil utilizing sulphonated bio-graphene catalysts for biodiesel production

Enhanced reaction performance is what has piqued interest in using graphene-based catalysts in producing biodiesel. However, in-depth analyses were lacking from a kinetic and thermodynamic standpoint. This means that a well-designed experiment is necessary to determine the effect that the graphene catalysts have on the reaction rates and yields. This work addresses the kinetic and thermodynamic aspects of heterogeneously catalyzed transesterification using sulphonated biomass-derived graphene catalysts, i.e., bGO-SO3H and brGO-SO3H. It was accomplished using the pseudo-first order mechanism and the Eyring-Polanyi equation, with all data fitting satisfactorily in both models at the ideal reaction temperature of 353.15 K, resulting in R2 values of 0.9784 (bGO-SO3H) and 0.9884 (brGO-SO3H). The calculated activation energy (Ea) was determined to be 44.45 and 51.73 kJ mol-1 for bGO- and brGO-SO3H, respectively. Additionally, the Gibbs free energy (ΔG) values were determined at −38.09 and −31.81 kJ mol−1 for bGO- and brGO-SO3H, respectively. Meanwhile, the values for ΔH and ΔS were obtained as 41.69 kJ mol−1 and 225.93 J mol−1 K−1, respectively, and 48.96 kJ mol−1 and 228.72 J mol−1 K−1, respectively. These collective outcomes collectively signify the endothermic nature of the reaction and their spontaneity, particularly under elevated temperature conditions.

Green energy breakthroughs: Harnessing nano-catalysts and enzymatic catalysts for bioenergy generation

Microbial fuel cells and anaerobic digestion are promising bioenergy methods but inefficient and scalable. With its exceptional surface area-to-volume ratio, nano-catalysts are revolutionizing this field. Researchers have improved energy conversion efficiency by immobilizing or embedding nanoparticles on electrodes or catalytic supports to promote electron transport. Nanomaterials like graphene-based catalysts and metal nanoparticles speed up organic matter breakdown and make bioenergy systems more profitable. Researchers are working harder to find new bioenergy-generating methods to address environmental concerns and the demand for sustainable energy. The study discusses how nano-catalysts and enzymatic catalysts are revolutionizing bioenergy production in green energy. Additionally, enzymatic catalysts are the best bioenergy catalysts. Highly specialized, biocompatible, and renewable enzymes provide unrivaled biofuel production potential. Protein engineering and immobilization have improved enzymes for bioenergy systems. Enzymatic catalysts enable biofuel generation from more feedstocks without harsh chemical procedures by controlling biological reactions quickly and precisely. Combining nano- and enzymatic catalysts is promising. Nano-catalysts improve enzymatic processes by creating a favorable microenvironment, enhancing surface binding sites, and enabling substrate transport. This combination may maximize bioenergy systems' biofuel output and wastewater treatment capabilities. According to this study, integrating nano- and enzymatic catalysts is a green energy breakthrough. These advances will improve bioenergy generation by overcoming current techniques, opening new sustainable energy production prospects, and expediting our transition to a greener, more sustainable future.

High-efficiency graphene-coated macroscopic composite for catalytic methane decomposition operated with induction heating

The large-scale production of hydrogen and the direct sequestration of carbon, in solid form, from the decomposition of natural gas could constitute an attractive economic alternative for the production of hydrogen if deactivation by coke or sintering could be mitigated. Here, we report on the use of a 2D graphene-based catalyst with controlled macroscopic shape for the catalytic decomposition of methane (CMD) at medium temperature, ranged from 500 °C to 900 °C, under contactless inductive heating. The presence of a magnetic field seems to have a strong influence on the catalytic performance and allows the maintain of the catalyst stability. Characterizations of the spent catalyst showed that the carbon deposited under inductive heating is in the form of carbon filaments which grow away from the edges or defects of the graphene. This particular growth mode allows one to maintain the catalytic activity of such carbon-based catalyst over longer periods compared to those reported in the literature. These promising results could set a base ground for the develop an industrially and economically viable way to convert natural gas into turquoise hydrogen, using renewable energy and low-cost catalysts, with improved resistance to poisoning by impurities present in the processing charge. The carbon formed could also be effectively use in other downstream applications. The combination of carbon-based catalyst and contactless induction heating could also lead to combined catalytic processes for numerous challenging reactions.

Catalytic mechanism of sulfur-nitrogen doping metal single-atom graphene-based catalysts for the conversion of CO2 to CH4: A computational study

The conversion of CO2 into renewable fuel (CH4) has significant environmental and economic benefits. Graphene-supported single-atom catalysts (SACs) show promise as electrocatalysts for the carbon dioxide reduction reaction (CO2RR). In this study, using spin-polarized density functional theory (DFT) calculations, we investigate the potential for converting CO2 to CH4 on the representative SACs, specifically graphene-supported TM-N-S (transition metal-nitrogen-sulfur). The results show that TM-N-S can break the scaling relationship between the adsorption energy of *CHO and *OCH2. The free energy profiles indicate that among the candidate TM-N-S SACs, Fe, Co, and Ni-N-S stand out with low overpotentials of 0.23, 0.40, and 0.39 V, respectively. Compared with the competing hydrogen evolution reaction (HER), they exhibit higher CO2 selectivity and catalytic activity. Analysis of electronic structure and charge variations reveals the origin of CO2RR activity and the binding strength between catalyst and intermediate. This work uncovers the potential mechanism of CO2RR, providing valuable insights into the conversion of CO2 to CH4 via TM-N-S catalysis and offering novel perspectives for the design and screening of efficient SACs for CO2RR.

Benchmarking a Molecular Flake Model on the Road to Programmable Graphene-Based Single-Atom Catalysts.

Single-atom catalysts (SACs) of embedding an active metal in nitrogen-doped graphene are emergent catalytic materials in various applications. The rational design of efficient SACs necessitates an electronic and mechanistic understanding of those materials with reliable quantum mechanical simulations. Conventional computational methods of modeling SACs involve using an infinite slab model with periodic boundary condition, limiting to the selection of generalized gradient approximations as the exchange correlation (XC) functional within density functional theory (DFT). However, these DFT approximations suffer from electron self-interaction error and delocalization error, leading to errors in predicted charge-transfer energetics. An alternative strategy is using a molecular flake model, which carved out the important catalytic center by cleaving C-C bonds and employing a hydrogen capping scheme to saturate the innocent dangling bonds at the molecular boundary. By doing so, we can afford more accurate hybrid XC functionals, or even high-level correlated wavefunction theory, to study those materials. In this work, we compared the structural, electronic, and catalytic properties of SACs simulated using molecular flake models and periodic slab models with first-row transition metals as the active sites. Molecular flake models successfully reproduced structural properties, including both global distortion and local metal-coordination environment, as well as electronic properties, including spin magnetic moments and metal partial charges, for all transition metals studied. In addition, we calculated CO binding strength as a descriptor for electrochemical CO2 reduction reactivity and noted qualitatively similar trends between two models. Using the computationally efficient molecular flake models, we investigated the effect of tuning Hartree-Fock exchange in a global hybrid functional on the CO binding strength and observed system-dependent sensitivities. Overall, our calculations provide valuable insights into the development of accurate and efficient computational tools to simulate SACs.

Graphene-based iron single-atom catalysts for electrocatalytic nitric oxide reduction: a first-principles study.

The electrocatalytic NO reduction reaction (NORR) emerges as an intriguing strategy to convert harmful NO into valuable NH3. Due to their unique intrinsic properties, graphene-based Fe single-atom catalysts (SACs) have gained considerable attention in electrocatalysis, while their potential for NORR and the underlying mechanism remain to be explored. Herein, using constant-potential density functional theory calculations, we systematically investigated the electrocatalytic NORR on the graphene-based Fe SACs. By changing the local coordination environment of Fe single atoms, 26 systems were constructed. Theoretical results show that, among these systems, the Fe SAC coordinated with four pyrrole N atoms and that co-coordinated with three pyridine N atoms and one O atom exhibit excellent NORR activity with low limiting potentials of -0.26 and -0.33 V, respectively, as well as have high selectivity toward NH3 by inhibiting the formation of byproducts, especially under applied potential. Furthermore, electronic structure analyses indicate that NO molecules can be effectively adsorbed and activated via the electron "donation-backdonation" mechanism. In particular, the d-band center of the Fe SACs was identified as an efficient catalytic activity descriptor for NORR. Our work could stimulate and guide the experimental exploration of graphene-based Fe SACs for efficient NORR toward NH3 under ambient conditions.

A first-principles study of electro-catalytic reduction of CO2 on transition metal-doped stanene.

Employing first-principles calculations based on density functional theory, this work examines the activity of 3d transition metal-doped stanene for electro-catalytic CO2 reduction through the first two electron transfer steps to CO. Our results related to CO2 activation, the first and a crucial step of the reduction process revealed that, among the entire 3d transition metal row studied, only Ti- and Fe-doped stanene can bind and significantly activate the CO2 molecule, while the rest of the TM single atoms are inert in activating the molecule. The activation of the CO2 molecule on Ti- and Fe-doped stanene has been observed in the presence of water as well. In addition, the formation of OCHO has been observed to be energetically preferred over COOH formation as a reaction intermediate, indicating the preference for the formate path of the reduction reaction. Furthermore, despite the strong adsorption of H2O on the catalyst surface, the presence of water seems to enhance CO2 adsorption on the catalysts, contrary to what has been observed recently in graphene-based catalysts. Finally, our difference charge density and the Bader charge calculations reveal that the ability of Ti- and Fe-doped stanene in activating the CO2 molecule and their potential catalytic activity for CO2 reduction is to be attributed to the charge transfer between the catalyst and the molecule, providing new insights into the rational design of 2D catalysts beyond graphene.

Boosting the oxygen reduction reaction activity of dual-atom catalysts on N-doped graphene by regulating the N coordination environment.

Development of low-cost and high-efficiency oxygen reduction reaction (ORR) catalysts is of significance for fuel cells and metal-air batteries. Here, by regulating the N environment, a series of dual-atom embedded N5-coordinated graphene catalysts, namely M1M2N5 (M1, M2 = Fe, Co, and Ni), were constructed and systematically investigated by DFT calculations. The results reveal that all M1M2N5 configurations are structurally and thermodynamically stable. The strong adsorption of *OH hinders the proceeding of ORR on the surface of M1M2N5, but M1M2N5(OH2) complexes are formed to improve their catalytic activity. In particular, FeNiN5(OH2) and CoNiN5(OH2) with the overpotentials of 0.33 and 0.41 V, respectively, possess superior ORR catalytic activity. This superiority should be attributed to the reduced occupation of d-orbitals of Fe and Co atoms in the Fermi level and the apparent shift of dyz and dz2 orbitals of Ni atoms towards the Fermi level after adsorbing *OH, thus regulating the active sites and exhibiting appropriate adsorption strength for reaction intermediates. This work provides significant insight into the ORR mechanism and theoretical guidance for the discovery and design of low-cost and high-efficiency graphene-based dual-atom ORR catalysts.

Advanced graphene-based (photo & electro) catalysts for sustainable & clean energy technologies

Due to the wide range of uses of graphene and its composites in electrocatalysis and photocatalysis, there has been a lot of interest in these materials.

Mechanistic understanding on effect of doping nitrogen with graphene supported single-atom Ir toward HER and OER: A computational consideration

The electrochemical hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) hold tremendous potential as pathways for generating clean energy. In this study, we conducted comprehensive density functional theory (DFT) calculations to investigate the influence of nitrogen (N) dopants, in terms of their types (Pyrrolic-N and Pyridinic-N) and concentrations, on the performance of 2D graphene-based catalysts containing single atoms of iridium (Ir SACs) for HER and OER. Our computational results demonstrate that the incorporation of N dopants into graphene-based supports significantly enhances the stability of Ir SACs. The bonding strength between the individual Ir atoms and the support material increases as the N content rises. Moreover, as the number of N dopants increases, the electron loss from Ir decreases. Notably, Ir-3-N1-Pi exhibits superior HER performance with a ΔGH* value of 0.24 eV, while Ir-4-N4-Po demonstrates excellent OER performance with an overpotential (η) of 0.47 V. By understanding the influence of N dopants, this study can pave the way for better tailor graphene-based catalysts for enhanced HER and OER performance, thus advancing the development of clean and sustainable energy technologies.

Facile dehydrogenation of MgH2 enabled by γ-graphyne based single-atom catalyst

Solid-state hydrogen storage is a promising roadmap for the safe and efficient utilization of hydrogen energy due to its moderate operating environment and high hydrogen storage density. However, as a representative solid-state hydrogen storage material, magnesium hydride (MgH2) is significantly limited in the commercial application due to its sluggish kinetics in the dehydrogenation process. Single-atom catalysts are a promising solution to this dilemma. However, the promising graphene-based single-atom catalysts are not yet sufficient to meet the dehydrogenation needs in engineering. To further address this dilemma, we designed a novel γ-graphyne based single-atom catalysts including eight 3d transition metals for promoting the dehydrogenation process of MgH2. Through using spin-polarized density functional theory calculations, we found that the energy barrier for MgH2 dehydrogenation has been significantly reduced even to 0.70 eV, which is far lower than the current graphene-based single-atom catalyst. In detail, the migration trajectory of hydrogen atom in the dehydrogenation process has been observed and confirmed using the ab initio molecular dynamics simulations. To investigate the intrinsic origin for its high catalytic activity of single-atom catalyst, we analyze the HMg bond activation mechanism through the electron localization function, charge density difference and crystal orbital Hamiltonian population. Finally, we found the relationship between energy barrier with electronic structure of single-atom catalyst, such as electrostatic potential and system electronegativity. This work can not only provide new ideas for the optimize of dehydrogenation catalyst, but also lay a theoretical foundation for the design of novel energy storage material.

Towards metal-free nitrogen-doped graphene aerogels as efficient electrocatalysts in hydrogen evolution reaction

Graphene-based materials have been researched to substitute traditional Pt-based electrocatalysts in the hydrogen evolution reaction (HER) due to its strong electrical conductivity, easy functionalization, and cheaper synthesis. Doping graphene with heteroatom is a simple way of obtaining original and active electrocatalysts. Moreover, the nitrogen on it had a positive effect on HER performance. By using a reducing agent with nitrogen while synthesising graphene-based aerogels nitrogen-doped catalysts were obtained. In addition, a better reduction rate, higher crystallography parameters and a more porous material structure were reached. The aerogels were synthesised in an one-pot hydrothermal process, in which the graphene sheets were assembled. This was followed by freeze-drying, which fixed the carbon matrix structure. As a result, the final aerogel had a 3D structure that eased mass transfer and enhanced catalytic activity, reaching an overpotential of −10 mAcm−2 at 101 mV vs RHE (η10 = 101 mV). The amount of quaternary type nitrogen generated during synthesis had a strong influence on electrocatalytic behaviour in HER. Then, quaternary nitrogen and surface area (up to 397 m2/g) were maximized to ensure a higher current density. Moreover, an effective aerogel was prepared with half the solvent per batch, as this was essential for expanding the synthesis to an industrial scale. A final calcination step resulted crucial to improve the metal-free aerogel HER performance.