Race on engineering noble metal single-atom electrocatalysts for water splitting

Constructing noble metal single-atom catalysts (NMSACs) is essential to boosting the water splitting electrocatalysis by virtue of their maximum atom utilization and distinctive electronic structure, which can concurrently reduce the usage of noble metal and maintain high catalytic activity. In the past few years, great progress has been achieved in the field of NMSACs, including the structure and local coordination environment modifications, which significantly promote the electrochemical performance toward water splitting and deepen the understandings of the underlying mechanisms. Herein, in this review, the recent advances of the NMSACs in the field of water splitting applications have been comprehensively summarized, with a special emphasis on the advantages, synthetic strategies, and characterizations of the NMSACs. Moreover, some representative examples regarding the applications of NMSACs toward water splitting are also manifested according to the theoretical and experimental results. Furthermore, the challenges and future potentials of the NMSACs are also manifested to offer guidance for the development of more advanced NMSACs.     

Study of activity and effectiveness factor of noble metal catalysts for water–gas shift reaction

Platinum on ceria-zirconia (CZO) catalysts for the water–gas shift (WGS) reaction were prepared with various platinum loadings. In addition, the activity of Pt/CZO catalysts was tested preliminarily at gas hourly space velocity (GHSV) of 5000 h⁻¹. Activity tests were also conducted at GHSV of 200,000 h⁻¹ with limited conversions, and activation energies and pre-exponential factors for rate equations were obtained by fitting the data. The effectiveness factors were estimated on the basis of the intra-particle mass transfer. Moreover, with this estimation, an attempt was made to calculate the utilization of the Pt loading with an eggshell morphology.     

Zr enhanced Fe,N, S co-doped carbon-based catalyst for high-efficiency oxygen reduction reaction

Fe-N_x catalysts have received widespread attention in recent years due to their excellent catalytic performance, hoping to replace platinum for oxygen reduction reactions (ORR). In recent years, more studies have shown that when the catalyst contains two or more metals doped, its catalytic performance will be improved. Herein, using the high temperature pyrolysis method, through the incorporation of the second phase metal (Zr), melamine as the nitrogen source, and thiourea as the sulfur source, a high-activity carbon-based catalyst doped with Fe and Zr bimetals was synthesized. Originating from the strong interaction between Fe species and ZrO₂ clusters and the promotion of O₂ adsorption by ZrO₂ nanoparticles supported on nitrogen-doped carbon, this catalyst has a better ORR electrocatalytic performance than 46% TKK commercial platinum carbon in 0.1 M KOH, exhibiting an onset potential of 1.047 V vs RHE, a half-wave potential of 0.909 V vs RHE. It provides a new idea for the preparation of high-performance bimetallic-doped carbon-based electrocatalysts.     

Steam reforming reactions over a metal-monolithic anodic alumina-supported Ni catalyst with trace amounts of noble metal

A trace amount of noble metal (Ru or Pt <0.1 wt%) was doped onto an anodic alumina-supported Ni catalyst, to investigate its performance in the steam reforming of methane (SRM), especially during DSS (daily startup and shutdown) operation. Although the steam purge treatment at high temperatures seriously deactivated the Ni catalyst because of the oxidation of metallic nickel with steam into Ni²⁺, trace Ru assisted the regeneration of active metallic nickel by hydrogen-spillover. And, the Ni sintering was largely alleviated by the addition of Ru, and it was probably due to the formation of Ru-Ni alloy. In comparison with the Ru-doped Ni catalyst, the Pt-doped Ni catalyst showed a more favorable tolerance to steam oxidation, even at 900 °C. In a stationary SRM test of 3000 h and a DSS SRM test of 500 times where the town gas 13A was used as hydrogen source, no obvious deterioration was detected over the Pt-doped Ni catalyst. Especially, when electrically heating the plate-type Pt-doped Ni catalyst to 700 °C, the SRM reaction system could reach a stable state within ca. 10 min, which offered a strong possibility to shorten the startup time from the 1-2 h of conventional reformer to just few minutes. In addition, the noble metal-doped Ni catalyst also showed favorable activity and durability when being applied to other steam reforming systems, such as kerosene and ethanol.     

SOFC anodes impregnated with noble metal catalyst nanoparticles for high fuel utilization

Redox-stable solid oxide fuel cell (SOFC) anodes are developed in order to improve durability at higher fuel utilization, as a possible alternative to conventional Ni-zirconia cermet anodes. Ce_0.9Gd_0.1O₂ (GDC) is utilized as a mixed ionic and electronic conductor (MIEC), in combination with Sr_0.9La_0.1TiO₃ (LST) as an electronic conductor. The stability of noble metals (Rh, Pt, and Pd) is analyzed via thermochemical calculation of stable phases. Noble metal catalyst nanoparticles are incorporated via co-impregnation with GDC. The electrochemical characteristics of SOFC single cells using these anode materials are investigated in highly-humidified H₂ at 800 °C. Their stability at high fuel utilization is analyzed. These co-impregnated anodes with highly dispersed noble metal catalysts on the LST-GDC conducting backbones, achieve high IV performance comparable to conventional Ni-cermet anodes. The co-impregnated anodes also achieve considerably high catalytic mass activity. At higher oxygen partial pressure, where the Ni catalyst can be deactivated by oxidation, these noble catalysts are thermochemically stable in the metallic state, and tolerant against oxidation. This class of alternative catalyst, impregnated with low-loading of noble metals could contribute to stable operation in the downstream region of SOFC systems. A simple cost analysis indicates a tolerance of using noble metals, provided their loading is sufficiently low.     

A comparative study of catalytic dehydrogenation of perhydro-N-ethylcarbazole over noble metal catalysts

N-ethylcarbazole is one of the most promising liquid organic hydrogen carriers (LOHCs) as it can be catalytically hydrogenated and dehydrogenated at relatively moderate temperatures. In the present work, we report a systematic study on dehydrogenation of perhydro-N-ethylcarbazole over several important supported noble metal catalysts to identify the optimal catalyst for temperature-controlled dehydrogenation. The reaction takes three consecutive stages with two intermediates of octahydro-N-ethylcarbazole and tetrahydro-N-ethylcarbazole. The initial catalytic activity of the selected noble metal catalysts for the dehydrogenation process was found to follow the order of Pd > Pt > Ru > Rh. 100% selectivity toward the final product of N-ethylcarbazole and fully dehydrogenation was achieved over the supported Pt and Pd catalysts. The kinetics of the three stage dehydrogenation processes over the catalysts was studied and the rate constants were derived. The results indicate that the dehydrogenation reaction rate decreases significantly with the reaction stage for all the selected noble catalysts and the conversion from tetrahydro-N-ethylcarbazole to N-ethylcarbazole was found to be the rate-limiting step of the entire reaction process.     

Combined dry reforming and partial oxidation of methane to synthesis gas on noble metal catalysts

In this paper CO₂ reforming of methane combined with partial oxidation of methane to syngas over noble metal catalysts (Rh, Ru, Pt, Pd, Ir) supported on alumina-stabilized magnesia has been studied. The catalysts were characterized by using BET, XRD, SEM, TEM, TPR, TPH and H₂S chemisorption techniques. The H₂S chemisorption analysis showed an active metal crystallite size in the range of 1.8-4.24 nm for the prepared catalysts. The obtained results revealed that the Rh and Ru catalysts showed the highest activity in combined reforming and both the dry reforming and partial oxidation of methane. The obtained results also showed a high catalytic stability without any decrease in methane conversion up to 50 h of reaction. In addition, the H₂/CO ratio was around 2 and 0.7 over different catalysts for catalytic partial oxidation and dry reforming, respectively.     

Autothermal reforming of ethanol on noble metal catalysts

Autothermal reforming of ethanol on zirconia-supported Rh and Pt mono- and bimetallic catalysts (0.5 wt-% total metal loading) was studied as a source of H₂-rich gas for fuel cells. The results were compared with those obtained on a commercial steam reforming catalyst (15 wt-% NiO/Al₂O₃). The Rh-containing catalysts exhibited the highest selectivity for H₂ production and were stable in 24 h experiments. The formation of carbonaceous deposits was lower on the noble metal catalysts than on the commercial NiO/Al₂O₃ catalyst. Thus, the Rh-containing catalysts are more suitable than the commercial NiO/Al₂O₃ catalysts for the ATR of ethanol.     

Advanced nickel metal catalyst for water-gas shift reaction

A comparative study has been performed to investigate the effectiveness of a Ni metal catalyst before and after impregnation with potassium for the water-gas shift (WGS) reaction. The potassium-modified Ni metal is both more active and more selective for the WGS reaction than the unmodified Ni catalyst. Furthermore, there is no carbon deposition on the modified Ni catalyst. The amount of H₂ produced and the CO conversion via WGS over the potassium-modified Ni catalyst are higher than those for the commercial high-temperature shift (HTS) catalyst under severe experimental conditions (gas-hourly space velocity = 80 000 h⁻¹, CO 60% and H₂ 40%). The suppression of methanation over the modified Ni metal is attributed to the action of the incorporated potassium in increasing the density of the active hydroxyl group that takes part in the WGS reaction to form the intermediate.     

Synergistic effect of metal components of the low-loaded Pt-Ni-Cr/C catalyst in the bicyclohexyl dehydrogenation reaction

The problem of hydrogen storage in liquid organic hydrogen carriers is not only the choice of an appropriate organic substrate, but the development of a selective and active catalyst containing as low as possible noble metals. A synergistic effect of increasing conversion and selectivity in bicyclohexyl dehydrogenation to biphenyl on trimetallic Pt-Ni-Cr/C catalysts with an extremely low Pt loading (0.1 wt %), compared with bimetallic Ni-Cr/C and Pt/Ni/C systems, due to the supporting of platinum on nickel-chromium nanoparticles was established for the first time. The TOF values (mmol (H₂)/g_Pt min) for hydrogen evolution under conditions of the reaction of bicyclohexyl dehydrogenation (320 °C, 0.1 MPa) on Pt supported onto a Ni-Cr/С composite exceed by two orders of magnitude the values found for the two-component catalysts. The maximum amount of the evolved hydrogen correlates to the selectivity of the complete dehydrogenation of bicyclohexyl into biphenyl on the Pt-Ni-Cr/C catalyst. The formation of a Ni-Cr solid substitution solution in a Ni-Cr composite deposited on a carbon carrier is shown by magnetometry, XRD, and TEM methods.     

Ni catalyst wash-coated on metal monolith with enhanced heat-transfer capability for steam reforming

A commercial Ni-based catalyst is wash-coated on a monolith made of 50 μm-thick fecralloy plates. Compared with the same volume of coarsely powdered Ni catalysts, the monolith wash-coated Ni catalysts give higher methane conversion in the steam reforming reaction, especially at gas hourly space velocities (GHSV) higher than 28,000 h⁻¹, and with no pressure drop. A higher conversion of the monolith catalyst is obtained, even though it contains a lower amount of active catalyst (3 g versus 17 g for a powdered catalyst), which indicates that the heat-transfer capability of the wash-coated Ni catalyst is significantly enhanced by the use of a metal monolith. The efficacy of the monolith catalyst is tested using a shell-and-tube type heat-exchanger reactor with 912 cm³ of the monolith catalyst charged on to the tube side and hot combusted gas supplied to the shell side in a counter-current direction to the reactant flow. A methane conversion greater than 94% is obtained at a GHSV of 7300 h⁻¹ and an average temperature of 640 °C. Nickel catalysts should first be reduced to become active for steam reforming. Doping a small amount (0.12 wt.%) of noble metal (Ru or Pt) in the commercial Ni catalyst renders the wash-coated catalyst as active as a pre-reduced Ni catalyst. Thus, noble metal-doped Ni appears useful for steam reforming without any pre-reduction procedure.     

Transition metal carbides coupled with nitrogen-doped carbon as efficient and stable Bi-functional catalysts for oxygen reduction reaction and hydrogen evolution reaction

Developing non-precious metal catalysts for oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) is crucial for proton exchange membrane fuel cell (PEMFC), metal-air batteries and water splitting. Here, we report a in-situ simple approach to synthesize ultra-small sized transition metal carbides (TMCs) nanoparticles coupled with nitrogen-doped carbon hybrids (TMCs/NC, including WC/NC, V₈C₇/NC and Mo₂C/NC). The TMCs/NC exhibit excellent ORR and HER performances in acidic electrolyte as bi-functional catalysts. The potential of WC/NC at the current density of 3.0 mA cm^?2 for ORR is 0.814 V (vs. reversible hydrogen electrode (RHE)), which is very close to Pt/C (0.827 V), making it one of the best TMCs based ORR catalysts in acidic electrolyte. Besides, the TMCs/NC exhibit excellent performances toward HER, the Mo₂C/NC only need an overpotential of 80 mV to drive the current density of 10 mA cm^?2, which is very close to Pt/C (37 mV), making it the competitive alternative candidate among the reported non-precious metal HER catalysts.     

Effect of noble metal addition over active Ru/TiO2 catalyst for CO selective methanation from H2 rich-streams

Selective CO methanation from H₂-rich stream has been regarded as a promising route for deep removal of low CO concentration and catalytic hydrogen purification processes. This work is focused on the development of more efficient catalysts applied in practical conditions. For this purpose, we prepared a series of catalysts based on Ru supported over titania and promoted with small amounts of Rh and Pt. Characterization details revealed that Rh and Pt modify the electronic properties of Ru. The results of catalytic activity showed that Pt has a negative effect since it promotes the reverse water gas shift reaction decreasing the selectivity of methanation but Rh increases remarkably the activity and selectivity of CO methanation. The obtained results suggest that RuRh-based catalyst could become important for the treatment of industrial-volume streams.     

Effect of transition metal (M: Fe,Co or Mn) for the oxygen reduction reaction with non-precious metal catalysts in acid medium

The effect of the metal for the oxygen reduction reaction (ORR) in acid medium with non-precious metal catalysts has been investigated. A series of non-precious metal catalysts with typical formulation M/N/C with M being Mn, Co or Fe have been prepared by incorporating N onto an active carbon matrix by means of thermal treatments under inert atmospheres. The N-containing active carbons were further treated with the M-containing precursors based upon Mn, Co or Fe phthalocyanines and thermally treated under inert atmosphere. The performance for the ORR in acid medium of all of the catalysts has been evaluated by means of electrochemical techniques. The activity, both in terms of onset potential for the ORR and maximum current density at representative potentials between 900 and 700 mV follows the trend Fe > Co > Mn. In addition, the performance of the Fe-based catalysts obtained during the different stages of the catalyst preparation has been also evaluated. The catalysts obtained after the pyrolysis step are the only ones showing measurable rates for the ORR. Although the amount of N and Fe incorporated onto the carbon matrix decreases the pyrolysis treatment, this treatment leads to the formation of the real active sites for the ORR irrespectively of the nature of the transition metal.     

Boosting the electrocatalytic performance of Pt,Pd and Au embedded within mesoporous cobalt oxide for oxygen evolution reaction

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CuCo2O4 microflowers catalyst with oxygen evolution activity comparable to that of noble metal

It is of high significance to design efficient, low-cost and durable electrocatalysts for the reaction (OER) in alkaline solution. In this communication, we report the development of CuCo₂O₄ microflowers directly on nickel foam (CuCo₂O₄/NF) as an efficient and durable electrocatalyst for OER. Such CuCo₂O₄/NF demands overpotential of only 296 mV to drive a geometrical catalytic current density of 20 mA cm^?2, 73 mV and 145 mV less than that for Co₃O₄/NF and NF, respectively, which are better than that of RuO₂/NF. Furthermore, CuCo₂O₄/NF presents an excellent long-term electrochemical durability maintaining the activity at overpotential of 240 mV for 10 h.     

Evaluation of reaction kinetics for the catalyst used in PCRD and study of channel affect on the same

Hydrogen mitigation strategies have gained importance for Nuclear reactors owing to damage caused to integrity of reactor containment by hydrogen fire in three major nuclear accidents of Three Miles Island, Chernobyl and Fukushima. One promising technology for hydrogen mitigation is deploying Passive Catalytic Recombiner Devices (PCRDs). Principle involved here is recombining hydrogen released during accident with oxygen from ambient air inside reactor containment on catalyst surface to form steam. Present work focuses on experimental evaluation of reaction kinetics associated with hydrogen-oxygen recombination on surface of indigenous PCRD catalyst developed for Indian Nuclear Power Plants. Behavior of catalyst plates stacked in parallel inside PCRD has also been evaluated. This effect is due to difference in migration mechanisms of reactants and products to and from the catalyst surface. Overall affect has been empirically approximated as single step Arrhenius equation. This is significant in modelling of PCRDs for faster containment analysis using CFD.     

Effects of composition on electrochemical properties of a non-precious metal catalyst towards oxygen reduction reaction

A family of non-precious metal catalysts, Co-PPy-TsOH/C, has been synthesized with different amount of pyrrole and p-toluenesulfonic acid (TsOH). Elemental contents of Co, N, C, S, H and O in the obtained catalysts have been measured with physicochemical techniques and the performance of these catalysts towards oxygen reduction reaction (ORR) have been evaluated with electrochemical techniques. Then, the results obtained have been discussed with principal component analysis and linear correlation analysis to find the correlation/anticorrelation between the composition and electrochemical properties. It is revealed that the used amount of pyrrole has much more apparent effect than TsOH on elemental contents in the Co-PPy-TsOH/C catalysts, while both of them influence the ORR activity and mechanism of the catalysts. Besides, the effects of the contents of each element on the electrochemical performance have also been analyzed to guide the future development of similar catalysts.     

Nickel nanocones as efficient and stable catalyst for electrochemical hydrogen evolution reaction

In this work, nickel nanocones (NNCs) were fabricated by single-step electrodeposition method. The NNCs were used as hydrogen evolution electrode and their electrocatalytic activity was compared with pure nickel film. Linear Sweep Voltammetry (LSV), Tafel polarization, Electrochemical Impedance Spectroscopy (EIS), Cyclic Voltammetry (CV) and chronopotentiometry in 1 M KOH were used for study of the electrocatalytic activity for hydrogen evolution reaction (HER). The active surface area was increased by formation of NNCs and hence, the electrocatalytic activity of nickel electrode was improved. Results indicate that the current density corresponding to the amount of evolved hydrogen of NNCs is five times more than pure nickel film formed in the Watts bath.