Carbon Support Research Articles

Highly Active NiRu/C Cathode Catalyst Synthesized by Displacement Reaction for Anion Exchange Membrane Water Electrolysis.

Anion exchange membrane water electrolysis (AEMWE) is highly promising for cost-effective green hydrogen production due to its basic operating conditions facilitating the use of non-noble catalysts. While non-noble Ni/Fe-based catalysts are utilized at the anode, its cathode catalyst still requires precious Pt. Due to the high cost of Pt and the sluggish hydrogen evolution reaction (HER) at the cathode in basic conditions, developing alternative catalysts to replace Pt is highly important. Here, a synthesis procedure for a Ru-based catalyst is reported and its high activity toward the HER in alkaline media is demonstrated in both half-cell and single-cell tests. The catalyst is synthesized in a two-step approach. A highly dispersed Ni catalyst is prepared on carbon support in the first step. In the second step, Ru is deposited on its surface using a galvanic displacement reaction. The uniqueness of this method is that Ru is deposited over the entire electrically conductive surface, resulting in an isotropic and homogeneous Ru distribution within the catalyst powder. It is demonstrated that this material remarkably outperforms state-of-the-art Pt/C catalysts in half-cell and single-cell tests. The single cell only requires 1.73V at 1A cm-2 with an overall PGM content of 0.05mg cm-2.

Ultra-High Activity and Durability of Low-Platinum Fuel Cells Enabled by Encapsulation of L10-PtCo and L12-Pt3Co Intermetallic Compounds.

Developing high-performance, durable, and ultralow-loading platinum (Pt) catalysts for the oxygen reduction reaction (ORR) is crucial for advancing fuel cells. Here, a novel structured alloy catalyst is reported, characterized by Pt-Co intermetallic compounds with a Pt-skin, encapsulated by a covalent organic framework (COF) derived carbon support. This unique structure, combining alloy-induced strain effects and protective encapsulation, leads to exceptional catalytic activity and stability at an ultralow Pt loading of 0.02 mgPt cm-2. To be specific, this catalyst exhibits peak power densities of 1.77W cm-2 in fuel cell tests. It demonstrates a state-of-the-art mass activity of 2.15 A mgPt -1 (@0.9 V), which is 5.38 times that of commercial Pt/C (0.40 A mgPt -1). More importantly, the fuel cell assembled with this novel catalyst displays exceptional durability, with a voltage degradation of only 9.9mV after 100,000 cycles at 0.8 A cm-2 and a mass activity retention of 85% (1.83 A mgPt -1), far exceeding the 2025 initial mass activity (MA) target (0.44 A mgPt -1) of DOE by 4.2 times. Notably, the current density at 0.6 V under hydrogen-air conditions shows only a slight decline after more than 230 h.

One-Step Synthesis of NiCo-LDH@Ni(OH)2 Heterostructure Foams on Biomass-Derived Porous Carbon for High-Performance Supercapacitors.

Layered double hydroxides (LDHs) have attracted much attention as pseudocapacitor supercapacitor electrodes because of their high theoretical specific capacity. However, LDHs have drawbacks such as poor electrical conductivity, and their specific capacities are lower than the theoretical values. In this work, NNCLDH@OPC electrodes are constructed via in situ synthesis of heterostructure foams (NNCLDH) consisting of NiCo-LDH and Ni(OH)2 on pomelo peel-derived porous carbon (OPC) through a one-step solvothermal method using ZIF-67 as a template. Owing to the synergistic effect of the 3D nanofoam structure and the multicomponent heterostructure as well as the conductive porous carbon support, the NNCLDH/OPC exhibited ultrahigh electrochemical performance as well as excellent cycling stability: a specific capacity of 3290 F g-1 at 1 A g-1 and a capacitance retention of 77.8% after 4000 cycles at a current density of 10 A g-1. In addition, the assembled NNCLDH@OPC//OPC asymmetric supercapacitor (ASC) has a maximum energy density of 51Wh kg-1 with a power density of 812W kg-1 and a maximum power density of 16kW kg-1 at a current density of 20 A g-1. These results demonstrate the significant application potential of NNCLDH/OPC composites in supercapacitor electrodes.

Aqueous Phase Reforming by Platinum Catalysts: Effect of Particle Size and Carbon Support

Aqueous Phase Reforming by Platinum Catalysts: Effect of Particle Size and Carbon Support

Assessment of the Impact of China's Carbon Emissions Trading Pilot Policy on the Export Product Quality

To achieve the "dual carbon" goals, China has established a carbon emissions trading market to reduce corporate carbon emissions through market mechanisms. The effect of China's carbon trading pilot programme on export product quality is examined in this study. The analysis employs the quasi-natural experiment provided by this policy, focusing on the quality of exported goods. From 2009 to 2016, panel data from 31 provinces and municipalities created a difference-in-differences (DID) model. This model allows for a comprehensive examination of the impact at the city, industry, and destination country levels. The results show that the quality of exported goods is much improved by the adoption of the carbon trading pilot programme. Additionally, the examination of heterogeneity shows that the influence of the policy is greatest in central cities, with less noticeable effects in the eastern and western areas. The report offers suggestions for advancing carbon trading policies at its conclusion, including the adoption of customized strategies that take into account the distinctive qualities of certain geographic areas. These recommendations are intended to maximise the effectiveness of the carbon trading system and support China's broader environmental and economic objectives.

Effect of N-Doped Carbon on the Morphology and Oxygen Reduction Reaction (ORR) Activity of a Xerogel-Derived Mn(II)O Electrocatalyst

This work synthesizes a xerogel from a sol–gel synthesis strategy and supports it on N-doped carbon support from spent coffee biomass (Mn(II)O/N-CC, hereafter MnO) as an efficient oxygen reduction reaction (ORR) catalyst in alkaline electrolytes. The effects of N-CC carbon content on MnO nanoparticle size, dispersion, distribution, morphology, and electrochemistry on ORR are discussed. The SEM and TEM measurements show that increasing the N-CC content during the MnO gelation reaction improved MnO dispersion and particle size during thermal treatment, increasing the ORR’s electrochemical active surface area. Several physiochemical and electrochemical characterizations show a clear relationship between N-CC catalysts and ORR activities. The best catalyst, MnO/N-CC-5, had an even distribution of 27 nm MnO nanoparticles on the N-CC support. The MnO/N-CC-5 catalyst had almost identical ORR kinetics and stability to those of the state-of-the-art Pt/C catalyst in 0.1 M KOH electrolytes, losing only 10 mV in half-wave potential after 5000 potential cycles and retaining 96% of current for over 10 h of continuous chronoamperometric stability. By measuring the electrochemical active surface areas of various catalysts by cyclic voltammetry at different scan rates and measuring the double layer capacitance (Cdl) and ECSA, MnO/N-CC-5 catalysts were shown to have enhanced ORR activity. The XPS analysis explains the ORR activity in terms of the Mn3+/Mn4+ ratio, and a mechanism was proposed. These findings suggest that the MnO/N-CC-5 catalyst could be a cathode catalyst in fuel cells, biofuel cells, metal–air batteries, and other energy conversion devices.

Modification of High-Surface-Area Carbons Using Self-Limited Atomic Layer Deposition

This study explores the application of Atomic Layer Deposition (ALD) to functionalize high-surface-area carbon supports with metal and metal oxide films and particles for applications in catalysis and electrocatalysis. The work reported here demonstrates that, through careful choice of precursors and absorption and reaction conditions, self-limited ALD growth on a high-surface-area carbon support can be achieved. Specific examples presented include the growth of conformal films of ZrO2 and SnO2 and the deposition of Ga2O3 and Pt particles on a carbon black support with a surface area of 250 m2·g−1. A novel strategy for controlling the Pt weight loading and producing sub-nanometer Pt particles on a carbon support using a single ALD cycle is also presented.

Insights into the effect of various supports on hydrothermal liquefaction of food waste over iron-oxide nano-catalysts

This work investigates the effect of supported iron-oxide nano-catalysts for hydrothermal conversion of food waste. The studied supports were Vulcan carbon (VC), CeO2, ZSM-5 and amorphous SiO2-Al2O3. Catalytic hydrothermal liquefaction experiments were carried out in a batch reactor at 16 MPa and 300 °C maintained for 1 h. Different fractions of Fe(0), Fe2+ and Fe3+ alter its tendency toward deoxygenation, hydrogenations and condensation reactions, which influence the bio-crude yield, elemental compositions, and energy recoveries. The fresh and spent catalysts were characterized using X-ray photoelectron spectroscopy, physisorption analysis, thermogravimetric analysis, transmission and scanning electron microscopy. It was found that the change in catalyst support influences HTL pathways and product compositions. The results reveal that the inclusion of FeOx catalyst on Vulcan carbon, SiO2-Al2O3 and ZSM-5 supports can increase the bio-crude yield by ~7–9 wt% compared to their FeOx-free yields. The increase in bio-crude yield was associated with the decrease in the surface ratios of Fe3+/Fe2+ at the range of 0.8–1.6. In overall, catalysts that had higher tendencies in converting amines into oil-soluble compounds increased the bio-crude yield, while catalysts that promoted dehydration and decarboxylation route decreased the bio-crude yield. The maximum energy recovery in bio-crude was obtained using FeOx/SiO2-Al2O3 catalyst with values ~95 %. The deactivation of catalysts was associated with the increase in Ca and P poisonous elements on catalytic sites, which decreased the energy recovery of recycled FeOx/SiO2-Al2O3 to ~85 % after three cycles.

The effect of carbon supports on the electrocatalytic performance of Ni-N-C catalysts for CO2 reduction to CO

Carbon-supported nickel and nitrogen co-doped (Ni-N-C) catalysts have been extensively studied as selective and active catalysts for CO2 electroreduction to CO. Most studies have focused on adjusting the coordination structure of Ni-Nx active sites, while the impact of the carbon supports has often been overlooked. In this study, a series of Ni-N-C catalysts on different carbon supports, including carbon black (CB), multi-walled carbon nanotubes (CNT), and activated nitrogen-doped biochar (ANBC), were synthesized using a ligand-mediated method. The effect of the carbon support on the electrocatalytic performance for CO2 reduction was investigated at both low current densities, in a H-cell, and high current densities, in a MEA electrolyzer. All of the prepared Ni-N-C catalysts show good faradaic efficiencies (FE) toward CO production (up to ~90%), however, the onset potentials and partial current densities for CO production vary greatly. The textural properties of the carbon support and the distribution of Ni-Nx active sites on the carbon support are demonstrated as the main factors behind the performance differences. In particular, hierarchical porous structures with large specific surface area are helpful to facilitate mass transport and improve the dispersion of active sites, which allows for a better CO2 reduction performance of Ni-N-ANBC compared to Ni-N-CB and Ni-N-CNT. This study demonstrates the importance of the carbon support for Ni-N-C catalysts and provides new insights into the design of efficient Ni-N-C catalysts for the CO2RR.

Carbon-anchoring synthesis of Pt1Ni1@Pt/C core-shell catalysts for stable oxygen reduction reaction

Proton-exchange-membrane fuel cells demand highly efficient catalysts for the oxygen reduction reaction, and core-shell structures are known for maximizing precious metal utilization. Here, we reported a controllable “carbon defect anchoring” strategy to prepare Pt1Ni1@Pt/C core-shell nanoparticles with an average size of ~2.6 nm on an in-situ transformed defective carbon support. The strong Pt–C interaction effectively inhibits nanoparticle migration or aggregation, even after undergoing stability tests over 70,000 potential cycles, resulting in only 1.6% degradation. The stable Pt1Ni1@Pt/C catalysts have high oxygen reduction reaction mass activity and specific activity that reach 1.424 ± 0.019 A/mgPt and 1.554 ± 0.027 mA/cmPt2 at 0.9 V, respectively, attributed to the optimal compressive strain. The experimental results are generally consistent with the theoretical predictions made by our comprehensive microkinetic model which incorporates essential kinetics and thermodynamics of oxygen reduction reaction. The consistent results obtained in our study provide compelling evidence for the high accuracy and reliability of our model. This work highlights the synergy between theory-guided catalyst design and appropriate synthetic methodologies to translate the theory into practice, offering valuable insights for future catalyst development.

Resolving optimal ionomer interaction in fuel cell electrodes via operando X-ray absorption spectroscopy

To bridge the gap between oxygen reduction electrocatalysts development and their implementation in real proton exchange membrane fuel cell electrodes, an important aspect to be understood is the interaction between the carbon support, the active sites, and the proton conductive ionomer as it greatly affects the local transportations to the catalyst surface. Here we show that three Pt/C catalysts, synthesized using the polyol method with different carbon supports (low surface area Vulcan, high surface area Ketjenblack, and biomass-derived highly ordered mesoporous carbon), revealed significant variations in ionomer-catalyst interactions. The Pt/C catalysts supported on ordered mesoporous carbon derived from biomass showed the best performance under the gas diffusion electrode configuration. Through a unique approach of operando X-ray Absorption Spectroscopy combined with gas sorption analysis, we were able to demonstrate the beneficial effect of mesopore presence for optimal ionomer-catalyst interaction at both molecular and structural level.

Fe-N catalyst derived from and supported on Lycopodium clavatum sporopollenin exine capsules for the oxygen reduction reaction

A carbon-supported electrocatalyst, featuring carbon nanotubes anchored on 3D porous graphitic carbon, was developed with the aim to perform in the operating conditions of alkaline fuel cells and metal air batteries. The catalyst was developed via two steps: first powders of Sporopollenin exine capsules used as a bio-based carbon support were activated via CO2 gasification to obtain a high specific area and porosity, second the derived porous carbons were impregnated by an iron salt and a nitrogen source, to be carbonised in Nitrogen at high temperature. The prepared catalyst demonstrated an efficient oxygen reduction reaction activity showing a half-wave potential of ~ 0.775 V vs. Reversible hydrogen electrode, comparable with that of commercial 20 wt% Pt/C in alkaline conditions, a good stability after accelerated degradation testing, retaining ~ 86% of the initial limiting current density, and a higher diffusion limited current density (6.3 vs. 5.1 mA cm− 2) than the commercial counterpart. Overall, we show the suitability of Sporopollenin exine capsule as support for electrocatalysis and a promising methodology to develop sustainable catalysts for the oxygen reduction reaction.

Study of Electron Beam Irradiated Palladium on Carbon Catalysts for Transfer Hydrogenation Reactions of Nitroarenes Compounds

Palladium-catalyzed hydrogenation is considered a crucial stage in the entire synthesis of difficult natural products as well as a crucial step in the manufacturing of fine compounds used in pharmaceuticals. When it comes to the reaction rate and simplicity of work-up, using Pd/C as heterogeneous catalyst is one of the best choice for process efficiency. In this study, nitroarenes compounds viz. 3-bromo nitrobenzene, 4-fluoro nitrobenzene, 3-methyl nitrobenzene, 4-hydroxy nitrobenzene reduced by using macro 10% Pd/C and micro 10% Pd/C to 3-bromo aniline, 4-fluoro aniline, 3-methyl aniline, 4-hydroxy aniline respectively and verified from 1H NMR studies. The reduction reactions were similar conditions using electron beam irradiated 250 kGy macro and micro 10% Pd/C catalyst. The effectiveness of commercial sources of palladium on carbon (Pd/C) varies widely, leading to the appreciable variations in the reaction times. The decrease in reaction time has been attributed to the higher dispersion of Pd particles upon irradiation. The physico-chemical characteristics of effective hydrogenation catalysts were determined to be: (i) small Pd particle size and (ii) homogeneous distribution of Pd on the carbon support. With no significant loss of catalytic activity, the electron beam-irradiated catalyst can be used again for five runs. These days, chemists can determine as well as forecast the effectiveness of catalysts before investing time and money in expensive synthetic materials.

Performance constraints of high temperature polymer electrolyte membrane fuel cells by varying the Pt/C ratio of the catalyst

Electrodes prepared from catalysts with Pt weight percentages on the carbon support (Pt/C nanoparticles) ranging from 10 up to 60 wt% are used as cathodes of membrane electrode assemblies (MEAs) and tested in high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). For each Pt/C percentage in the catalyst, the cathode Pt-loading (which become proportional to the thickness of the electrode formed by the catalyst nanoparticles) is stepwise scanned from low to high loadings. Results show that when the Pt load increases, the MEA performance (measured by its power density at 0.6 V) rises initially (due to the increase in the number of active sites in the cathode) up to a maximum value limited by the mass transport of oxygen, associated to an optimum Pt-loading (different for each Pt/C ratio). Noteworthy, the peak performance is significantly different depending on the catalyst used (60 > 40 >> 20 > 10 wt% Pt/C), a fact that restricts the catalyst choice according to the performance required by the application. Furthermore, higher amounts of Pt in the cathode lead to a large catalyst waste as the FC performance even decreases as the cathode thickness increases.

C60 Fullerene‐Induced Reduction of Metal Ions: Synthesis of C60‐Metal Cluster Heterostructures with High Electrocatalytic Hydrogen‐Evolution Performance

AbstractMetal clusters, due to their small dimensions, contain a high proportion of surface atoms, thus possessing a significantly improved catalytic activity compared with their bulk counterparts and nanoparticles. Defective and modified carbon supports are effective in stabilizing metal clusters, however, the synthesis of isolated metal clusters still requires multiple steps and harsh conditions. Herein, we develop a C60 fullerene‐driven spontaneous metal deposition process, where C60 serves as both a reductant and an anchor, to achieve uniform metal (Rh, Ir, Pt, Pd, Au and Ru) clusters without the need for any defects or functional groups on C60. Density functional theory calculations reveal that C60 possesses multiple strong metal adsorption sites, which favors stable and uniform deposition of metal atoms. In addition, owing to the electron‐withdrawing properties of C60, the electronic structures of metal clusters are effectively regulated, not only optimizing the adsorption behavior of reaction intermediates but also accelerating the kinetics of hydrogen evolution reaction. The synthesized Ru/C60‐300 exhibits remarkable performance for hydrogen evolution in an alkaline condition. This study demonstrates a facile and efficient method for synthesizing effective fullerene‐supported metal cluster catalysts without any pretreatment and additional reducing agent.

Effects of carbon support ozonation on the electrochemical reduction of CO2 to formate and syngas in a flow cell on Pd nanostructures

Pd convers electrochemically CO2 into formate at the most positive known potentials but with low activity. Additionally, Pd is CO selective at more negative potentials, but is poisoned by the strongly bound CO∗ intermediate. Improving the activity and stability of Pd-based electrocatalysts holds promise for improving the electrochemical production of formic acid. Herein, we studied the effects of carbon support and its ozonation on the selectivity of electrochemical CO2 reduction on Pd. The ozone treatment is found to improve the activity and formate selectivity at low overpotentials on single-walled carbon nanotube-supported catalysts with partial current densities up to −12 mA cm−2 in 0.5 M KHCO3 at potentials of −0.35 V and −0.45 V (vs. RHE). At more negative potentials, the catalysts become more selective towards CO and an opposite trend for CO-selectivity and ozonation duration is demonstrated. Unfortunately, the materials show deactivation in the form of decreased formate selectivity and increased hydrogen and CO evolution, especially when supports treated with ozone for a longer duration. The results and possible mechanisms are discussed based on previous findings and the physicochemical characterizations of the prepared catalysts. This work shows that a simple ozone treatment of carbons changes the efficiency of CO2 electroreduction.

Porous Carbon‐Supported Catalysts for Proton Exchange Membrane Fuel Cells

AbstractProton exchange membrane fuel cells (PEMFCs) are crucial for the efficient utilization of hydrogen. Currently, their efficiency is mainly limited by the slow kinetics of the cathode oxygen reduction reaction (ORR) and the poisoning effect between ionomers and catalytic sites, particularly with Pt‐based catalysts. Recent works suggest that the emerging porous carbon‐supported catalysts hold promise in mitigating these challenges by ensuring fast kinetics while alleviating the poisoning. This review examines porous carbon‐supported catalysts for PEMFC cathodes, covering synthesis methods, structure and performance evaluation, and future prospects, with an emphasis on the influence of porous carbon support on PEMFC performance. On one hand, the rational design of pore structure in carbon support can help optimize the location of the active sites and enhance mass transfer. On the other hand, diverse pore structures provide a platform for gaining a deeper understanding of the mechanisms behind microscale mass transfer and reaction at the three‐phase boundaries. This review aims to inspire innovative strategies for the precise synthesis of porous carbon‐supported catalysts with various pore structures to further boost PEMFC performance.

Upside-Down Adsorption: The Counterintuitive Influences of Surface Entropy and Surface Hydroxyl Density on Hydrogen Spillover.

Although hydrogen spillover is often invoked to explain anomalies in catalysis, spillover remains a poorly understood phenomenon. Hydrogen spillover (H*) is best described as highly mobile H atom equivalents that arise when H2 migrates from a metal nanoparticle to an oxide or carbon support. In the 60 years since its discovery, few methods have become available to quantify or characterize H*-support interactions. We recently showed in situ infrared spectroscopy and volumetric chemisorption can quantify reversible H2 adsorption on Au/TiO2 catalysts, where adsorbed hydrogen exists as H* and interacts with titania surface hydroxyl (TiOH) groups. Here, we report parallel thermogravimetric analysis and Fourier transform infrared spectroscopy methods for systematically manipulating the surface TiOH density. We examine the role of surface hydroxylation on spillover thermodynamics using van't Hoff studies to determine apparent adsorption enthalpies and entropies at constant H* coverage, which is necessary to maintain constant H* translational entropy. Although surface TiOH groups are the likely adsorption sites, the data show removing hydroxyl groups increases spillover. This surprising finding─that adsorption increases as the adsorption site density decreases─is associated with improved thermodynamics on dehydroxylated surfaces. A strong adsorption enthalpy-entropy correlation implicates the changing surface entropy of the titania support itself (i.e., an initial state effect) is deeply intertwined with the H* configurational entropy. These effects are surprising and should apply to all low-coverage adsorbates where entropy terms dominate more traditional enthalpic considerations. Moreover, this study points toward a kinetic test for invoking spillover in a reaction mechanism: namely, in situ dehydroxylation should enhance spillover processes.

Unveiling the Aggregation of M-N-C Single Atoms into Highly Efficient MOOH Nanoclusters during Alkaline Water Oxidation.

M-N-C-type single-atom catalysts (SACs) are highly efficient for the electrocatalytic oxygen evolution reaction (OER). And the isolated metal atoms are usually considered real active sites. However, the oxidative structural evolution of coordinated N during the OER will probably damage the structure of M-N-C, hence resulting in a completely different reaction mechanism. Here, we reveal the aggregation of M-N-C materials during the alkaline OER. Taking Ni-N-C as an example, multiple characterizations show that the coordinated N on the surface of Ni-N-C is almost completely dissolved in the form of NO3 -, accompanied by the generation of abundant O functional groups on the surface of the carbon support. Accordingly, the Ni-N bonds are broken. Through a dissolution-redeposition mechanism and further oxidation, the isolated Ni atoms are finally converted to NiOOH nanoclusters supported by carbon as the real active sites for the enhanced OER. Fe-N-C and Co-N-C also have similar aggregation mechanism. Our findings provide unique insight into the structural evolution and activity origin of M-N-C-based catalysts under electrooxidative conditions.

Defective carbon-bridged Cu sites to boost oxygen reduction reaction in neutral zinc-air batteries

Novel carbon nanomaterials containing N-coordinated metal centers present an advantage in promoting the oxygen reduction reaction (ORR). Despite considerable progress, substantial challenges persist with the advancement of neutral Zinc-air batteries (ZABs), particularly in optimizing the trade-off between the catalytic activity and stability. Herein, employing nanoporous carbon impregnated with Cu(II)-phenanthroline complexes to prepare Cu-ONCs catalysts rich in Cu-Nx sites. Controllable carbon defects to capture Cu2+ enable the enrichment of metal sites on the porous carbon surface, and simultaneously effectively suppress the aggregation of active centers. The metal moieties, specifically Cu-Nx, are incorporated into the porous N-doped carbon, thereby introducing accessible active sites within the partially graphitized carbon framework. Furthermore, the abundant mesopores inside the carbon nanofibers promote the exposure of accessible active sites to substantially augment the electrochemically active electrochemically active area area. Given the unique structure and composition, Cu-ONCs show outstanding ORR activity in neutral and alkaline media, alone with negligible decay observed after 3000 cycles. Moreover, Cu-ONCs based neutral ZABs demonstrate a peak power density of 48.28 mW cm−2 and impressive rate performance. This work provides defects/vacancies insight on transition metal (TM)-based carbon support to facilitate the advancement of cutting-edge neutral ZABs.