Copper(II) phthalocyanine/metal organic framework electrocatalyst for hydrogen evolution reaction application

Copper(II)phthalocyanine-incorporated metal organic framework (CuPc/MOF) composite material was synthesized for application as an electrocatalyst for hydrogen evolution reaction (HER). The composite exhibited excellent electroactivity compared to the unmodified MOF, as confirmed by the diffusion coefficients (D) values of 3.89 × 10⁻⁷ and 1.57 × 10⁻⁶ cm² s⁻¹ for MOF and CuPc/MOF, respectively. The D values were determined from cyclic voltammetry (CV) experiments performed in 0.1 mol L⁻¹ tetrabutylammonium perchlorate/dimethyl sulfoxide (TBAP/DMSO) electrolyte. The Tafel slope determined from the CV data of CuPc/MOF-catalysed HER for 0.450 mol L⁻¹ H₂SO₄, was 176.2 mV dec⁻¹, which was higher than that of the unmodified MOF (158.3 mV dec⁻¹). The charge transfer coefficients of MOF and CuPc/MOF were close to 0.5, signifying the occurrence of a Volmer reaction involving either the Heyrovsky or the Tafel mechanism for hydrogen generation. For both MOF and CuPc/MOF, the exchange current density (i₀) improved with increase in the concentration of the hydrogen source (i.e. 0.033–0.45 mol L⁻¹ H₂SO₄) Nonetheless, the CuPc/MOF composite had a higher i₀ value compared with the unmodified MOF. Thus CuPc/MOF has promise as an efficient electrocatalyst for HER.     

Boosting the activity of FeOOH via integration of ZIF-12 and graphene to efficiently catalyze the oxygen evolution reaction

Transition metal oxyhydroxides have been used as promising electrocatalysts for water splitting however, their catalytic activity is restricted due to low surface area and poor conductivity. Herein, we report novel composite FeOOH@ZIF-12/graphene composite as electrocatalyst for water oxidation, whereby ZIF-12 provide extra surface for the FeOOH dispersion whilst graphene act as excellent electron mediator. The composite shows a low overpotential value of 291 mV to attain a current density of 10 mA cm^?2 and a low Tafel slope value of 78 mV dec^?1. The catalyst offers a maximum current density of 101 mA cm^?2, while it gives a turnover frequency (TOF) value of 0.031 s^?1 at an overpotential of 291 mV only. The excellent activity and remarkable stability of composite is attributed to highly conductive and porous support.     

Constructing Ni-Modified Co-FcDA nanosheets for enhancing electrocatalytic oxygen evolution reaction

Electrocatalytic water splitting is an emerging technology for the development of maintainable hydrogen energy. It remains challenging to manufacture a stable, efficient, and cost-effective electrocatalyst that can conquer the slow reaction kinetics of water electrolysis. Herein, A metal-organic framework (MOF) based material is manufactured and productively catalyze the oxygen evolution reaction (OER). The introduction of elemental nickel enhances the catalytic activity of Co-FcDA. The results show that single Ni was well doped in the CoNi-FcDA catalysts and the doping of Ni has a great influence on the OER activity of CoNi-FcDA catalysts. CoNi-FcDA displayed a low overpotential of 241 mV to arrive at the benchmark current density (10 mA cm^?2) with a remarkably small Tafel slope of 78.63 mV dec^?1. It surpassed the state-of-the-art electrocatalyst for OER, that is, RuO₂ (260 mV and 97.26 mV dec^?1) in efficiency as well as instability. Density functional theory (DFT) calculations show that suitable Ni doping at the same time can increase the density of states of the Fermi level, resulting in excellent charge density and low intermediate adsorption energy. These discoveries provide a practical route for designing 2D polymetallic nanosheets to optimize catalytic OER performance.     

A dotted nanowire arrayed by 5 nm sized palladium and nickel composite nanopaticles showing significant electrocatalytic activity towards ethanol oxidation reaction (EOR)

To the best of our knowledge, this is the first time to report the preparation of a dotted nanowire arrayed by 5 nm sized palladium and nickel composite nanoparticles (denoted as Pd_xNi_y NPs) via a hydrothermal method using NU and PdO·H₂O as the starting materials. The samples prepared at the mass ratio of NU to PdO·H₂O 1:1, 1:2 and 2:1 were, respectively, nominated as catalyst c₁, c₂ and c₃. The chemical compositions of all synthesized catalysts were mainly studied by using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), revealing that metallic Ni was one main component of all prepared catalysts. Surprisingly, the main diffraction peaks appearing in the XRD patterns of all prepared catalysts were assigned to the metallic Ni rather than the metallic Pd. Very interestingly, as indicated by the TEM images, a large number of dotted nanowires arrayed by numerous equidistant 5 nm sized nanoparticles were distinctly exhibited in catalyst c₁. More importantly, when being used as electrocatalysts for EOR, all prepared catalysts exhibited an evident electrocatalytic activity towards EOR. In the cyclic voltammetry (CV) test, the peak current density of the forward peak of EOR on catalyst c₁ measured at 50 mV s^?1 was as high as 56.1 mA cm^?2, being almost 9 times higher than that of EOR on catalyst c₃ (6.3 mA cm^?2). Particularly, the polarized current density of EOR on catalyst c₁ at 3600 s, as indicated by the chronoamperometry (CA) experiment, was still maintained to be around 1.47 mA cm^?2, a value higher than the latest reported data of 1.3 mA cm^?2 (measured on the pure Pd/C electrode). Presenting a novel method to prepare dotted nanowires arranged by 5 nm sized nanoparticles and showing the significant eletrocatalytic activities of the newly prepared dotted nanowires towards EOR were the major contributions of this preliminary work.     

Adjusting electronic structure coupling of Fe–Ni2P (NiFeP-MOF) multilevel structure for ultra-activity and durable catalytic water oxidation

Efficient electrocatalyst for alkaline oxygen evolution reaction is the critical core to the wide application of metal-air energy storage and water electrolysis hydrogen energy. Therefore, appropriate design of highly active and stable non-noble metal oxygen evolution electrocatalyst with good electronic structure and multilevel structure is both a goal and a challenge. Here, we report a Fe–Ni₂P electrocatalyst (NiFeP-MOF) with multilevel structure, which was obtained by anion exchange on the basis of Fe–Ni(OH)₂ (NiFe-MOF) grown on nickel foam in situ by solvothermal method. As expected, Fe substitution regulates the Ni oxidation state in the NiFeP-MOF and realizes electronic structure coupling, showing a highly active and stable oxygen evolution reaction (OER) in alkaline electrolyte solution. Specifically, the NiFeP-MOF demonstrates an ultralow overpotentials (232 mV, 10 mA cm^?2; 267 mV 100 mA cm^?2), respectively, an extremely small Tafel slope (34 mV dec^?1). Separately, the electrocatalyst shows an excellent cycle stability at 10 mA cm^?2 for 12 h (43,200 s). More importantly, this work come up with an available policy for the preparation of excellent alkaline hydrolysis electrolysis catalysts and air cathodes with excellent performance.     

Bimetallic PtPd nanoparticles relying on CoNiO2 and reduced graphene oxide as a most operative electrocatalyst toward ethanol fuel oxidation

Of late, fuel cells have drawn great attentions owing to high-energy demands, fossil fuel depletion and worldwide environmental pollution. Direct ethanol fuel cell (DEFC) constituted as one of the most promising sources of green energy, howbeit the ethanol oxidation reaction (EOR) sluggish kinetic is one of the essential challenges toward the commercialization of DEFCs. Herein, we introduce bimetallic catalyst on CoNiO₂ modified reduced graphene oxide (rGO) to completely exploit the advantages of nano-surface structures as well as the reduction of Pt and Pd loading in fuel cells. With the combined advantages of PtPd, CoNiO₂ and rGO, a significant enhancement in electrocatalytic behavior, stability and CO poisoning tolerance of PtPd have been observed. Regarding the implications, PtPd/CoNiO₂/rGO is greatly preferable than Pt/CoNiO₂/rGO and Pd/CoNiO₂/rGO in terms of high electroactive surface area (ECSA), electro-catalytic activity, and lower onset potential (E_ons) towards the EtOH oxidation in alkaline media. Furthermore, the chronoamperometry curve (CA) illustrated 77% after 3600 s which is dramatically soared compared with the other electrodes (≤40%), demonstrating the high stability of the PtPd bimetallic nanoparticle electrocatalyst. Ultimately, PtPd/CoNiO₂/rGO nanocomposite is found to be an excellent anode electrocatalyst for application in DEFCs.     

A nano-spherical structure Ni3S2/Ni(OH)2 electrocatalyst prepared by one-step fast electrodeposition for efficient and durable water splitting

Developing non-noble metal catalysts with excellent electrocatalytic performance and stability is of great significance to hydrogen production by water electrolysis, but there are still problems of low activity, complex preparation and high cost. Herein, we fabricated a novel Ni₃S₂/Ni(OH)₂ dual-functional electrocatalyst by a one-step fast electrodeposition on nickel foam (NF). While maintaining the electrocatalytic performance of Ni₃S₂, the existence of heterostructure and Ni(OH)₂ co-catalyst function greatly improves the overall water splitting performance of Ni₃S₂/Ni(OH)₂–NF. Hence, It shows a low overpotential of 66 mV at 10 mA cm^?2 for HER and 249 mV at 20 mA cm^?2 for OER. The dual-functional electrocatalyst needs only 1.58 V at 20 mA cm^?2 when assembled two-electrode electrolytic cell. Impressively, the electrocatalyst also shows outstanding catalytic stability for about 800 h when 20 and 50 mA cm^?2 constant current was applied, respectively which demonstrates a potential electrocatalyst for overall water splitting.     

Co-based MOF-derived Co/CoN/Co2P ternary composite embedded in N- and P-doped carbon as bifunctional nanocatalysts for efficient overall water splitting

In this work, we developed ternary metallic cobalt-cobalt nitride-dicobalt phosphide composite embedded in nitrogen and phosphorus co-doped carbon (Co/CoN/Co₂P-NPC) as bifunctional catalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The as-prepared Co/CoN/Co₂P-NPC is achieved by simultaneous annealing and phosphating of a Co–N rich metal-organic frameworks (MOFs) precursor. Compare with the phosphorus-free Co/CoN embedded nitrogen-doped carbon electrocatalyst (Co/CoN-NC), the as-prepared Co/CoN/Co₂P-NPC display superior HER and OER low overpotential of 99 mV and 272 mV at current density of 10 mA cm⁻². When Co/CoN/Co₂P-NPC electrocatalyst is use as bifunctional catalysts in overall alkaline water splitting, it exhibit excellent behaviour with 10 mA cm⁻² current at overall cell potential of 1.60 V. The excellent performance of Co/CoN/Co₂P-NPC electrocatalyst is attributed to the phosphating process that could further enhance synergistic effect, create stronger electronic interactions, and form efficient dual heteroatom doping to optimize the interfacial adhesion within the electrocatalyst. This present work will create more opportunities for the development of new, promising and more active sites electrocatalysts for alkaline electrolysis.     

Multi-active site CoNi-MOFs as non-noble bifunctional electrocatalysts for highly efficient overall water splitting

The high-efficiency non-precious metal catalysts for oxygen evolution (OER) and hydrogen evolution (HER) are of great significance to the development of renewable energy technologies. Herein, a multiple active sites CoNi-MOFs-DBD electrocatalyst modified by low temperature plasma (DBD) was successfully synthesized by converting metal hydroxyfluoride on nickel foam into a well-arranged MOFs array using vapor deposition. The as-prepared CoNi-MOFs-DBD electrode showed better HER and OER catalytic activity, super hydrophilicity, and excellent stability. In an alkaline medium, the overpotential of HER is 203 mV at 10 mA cm^?2 and that of OER is 168 mV at 40 mA cm^?2. When CoNi-MOFs-DBD was used as a bifunctional electrocatalyst for overall water splitting in a two-electrode system, a current density of 10 mA cm^?2 can be achieved at a low voltage of 1.42 V, which shows great potential in electrocatalytic water splitting.     

Remarkable electrocatalytic activity of Ni-nanoparticles on MOF-derived ZrO2-porous carbon/reduced graphene oxide towards methanol oxidation

In the present work, a porous carbonaceous platform containing zirconium oxide was used for spreading Ni nanoparticles, and applied to methanol oxidation. The platform was obtained by calcination of a metal-organic framework (MOF) attached to graphene oxide. Nickel nanoparticles were then deposited on the nanocomposite by chemical reduction from a Ni²⁺ solution. The obtained electrocatalyst was characterized by different methods. An excellent electrocatalytic behavior was observed towards methanol oxidation in alkaline medium (j ~ 240 mA cm^?2 or ~ 626 mA mg^?1 in 1.0 M methanol). The results of methanol oxidation by various electrochemical studies (cyclic voltammetry, electrochemical impedance spectroscopy, chronoamperometry and chronopotentiometry) revealed the effective synergy between reduced graphene oxide, porous carbon material, ZrO₂ metal oxide and Ni nanoparticles. Good durability and stability of the proposed electrocatalyst and significantly increased current density of methanol oxidation suggest it as a potential alternative for Pt-based electrocatalysts in direct methanol fuel cells.     

Design the PdCu/Ni2P electrocatalyst with high efficiency for ethanol oxidation reaction in alkaline media

To facilitate the electrocatalytic behavior of Direct Ethanol Fuel Cells (DEFCs), a sequence of bimetallic Pd_xCu_y/Ni₂P-C catalysts are synthesized via the microwave-assisted ethylene glycol reduction method. The results indicate that our designed Pd₂Cu/Ni₂P-C(1:1) catalyst owns high activity (3974.08 mA mg^?1_Pd), 8.3 times higher than the commercial Pd/C. The durability and the CO tolerance of the corresponding catalysts are also investigated by chronoamperometry (CA) and CO stripping measurements, implying Pd₂Cu/Ni₂P-C(1:1) shows good durability and the anti-CO poisoning ability for EOR in alkaline media. The electrochemical impedance spectra (EIS) analysis reveals lower charge transfer resistance for Pd₂Cu/Ni₂P-C(1:1). Combined with the results of XRD, HRTEM, XPS and electrochemical measurements, we found that the good electrocatalytic activity, CO tolerance and long-term durability of Pd₂Cu/Ni₂P-C(1:1) may be provided by the electronic and strain effect among Pd, Cu and Ni₂P, which will bring the downshift in the d-band center of catalysts and the weakened adsorption of intermediates.     

Bifunctional electrocatalysts for water splitting from a bimetallic (V doped-NixFey) Metal–Organic framework MOF@Graphene oxide composite

An ongoing challenge still lies in the exploration of proficient electrocatalysts from earth-abundant non-precious metals instead of noble metal-based catalysts for clean hydrogen energy through large-Scale electrochemical water splitting. However, developing a non-precious transition metals based, stable electrocatalyst for cathodic hydrogen evolution reaction (HER) and anodic oxygen evolution reaction (OER) is important challenge for modern energy conversion technology. In this report Vanadium doped bimetallic nickel-iron nanoarray, fabricated by carbon supported architecture through carbonization process for electrochemical water splitting. Three types of catalysts were prepared in different molar ratio of Ni/Fe. The electrocatalytic performance demonstrated that the catalyst with equal mole ratio (0.06:0.06) of Ni/Fe possess high catalytic activity for both OER and HER in alkaline and acidic medium. Besides, our findings revealed that the doping of vanadium could play a strong synergetic effect with Ni/Fe, which provide a small overpotential of 90 mV and 210 mV at 10 mA cm^?2 for HER and OER respectively compared to the other two catalyst counterparts. Also, the catalyst with 1:1 (Ni/Fe) molar ratio showed a high current density of 208 mA cm^?2 for HER at 0.5 M H₂SO₄ and 579 mA cm^?2 for OER at 1 M KOH solution, the both current densities are much higher than the other two catalysts (different Ni/Fe ratio). In addition, the presented catalysts showed extremely good durability, reflecting in more than 20 h of consistent Chronoamprometry study at fixed overpotential η = 250 mV without any visible voltage elevation. Similarly, the (Ni/Fe) equal ratio catalyst showed better corrosion potential 0.209 V vs Ag/AgCl and lower current density 0.594 × 10^?12 A cm^?2 in high alkaline medium. The V-doping, MOF/GO surface defects are significantly increased the corrosion potential of the V-Ni_xFe_y-MOF/GO electrocatalyst. Besides, the water electrolyzed products were analysed by gas chromatography to get clear insights on the formed H₂ and O₂ products.     

Flower-like MOF-derived Co–N-doped carbon composite with remarkable activity and durability for electrochemical hydrogen evolution reaction

Electrochemical hydrogen evolution reaction (HER) is one of the most economical, sustainable, and attractive methods to produce hydrogen. Contemporarily, it is still a challenge to develop low-cost catalysts with high activity and durability for HER. Herein, we report a simple strategy to develop a Co–N-doped carbon electrocatalyst derived from a new cobalt metal-organic framework (MOF). The new flower-like 2D→3D MOF {[Co(BIPA)(5-OH-bdc)](DMF)}_n (1) was constructed based on bis(4-(1H-imidazol-1-yl)phenyl)amine (BIPA) and 5-hydroxyisophthalic acid (5-OH-H₂bdc). After that, the Co–N-doped carbon composite Co-MOF-800 was prepared via calcination of MOF 1. Interestingly, Co-MOF-800 exhibited excellent electrocatalytic activity and durability for HER. The onset potential (0.12 V) and E_j=10 value (0.193 V) of the Co-MOF-800 electrode were comparable to that of the most active non-precious metal HER electrocatalysts derived from other MOFs. The HER performance of Co-MOF-800 was stable without degradation even after long-term cycling.     

Pt electrodeposited on CeZrO4/MCNT as a new alternative catalyst for enhancement of ethanol oxidation

Electrocatalytic preparation of Pt-based nanocomposites has been investigated for improvement of direct ethanol fuel cells (DEFCs). In this study, new alternative catalysts of Pt-decorated cerium zirconium oxide-modified multiwalled carbon nanotubes (Pt/CeZrO₄/MCNT) were successively prepared to improve the activity of the ethanol oxidation reaction (EOR). The prepared CeZrO₄ with a face-centered cubic (fcc) structure compatibly dispersed onto MCNT provides abundant active Pt sites for highly active catalysts. The fcc-structured Pt was also satisfactorily decorated onto CeZrO₄/MCNT, resulting in highly active Pt. The Ce⁴⁺/Ce³⁺ redox property can promote oxygen vacancies to improve the electrochemical activity for oxidation of carbonaceous species. An increase in roughness and a stabilized catalyst structure can also be produced by inserting Zr⁴⁺ into the ceria metal oxide. The prepared Pt/20%CeZrO₄/MCNT catalysts present excellent electrochemical active surface area, mass activity, CO tolerance and high electron kinetic transfer with low resistance and high stability over commercial PtRu/C toward EOR. This promising catalyst material could be introduced to enhance the anodic oxidation reaction in DEFCs.     

High active and ultra-stable bifunctional FeNi/CNT electrocatalyst for overall water splitting

Efficient non-noble metal catalysts are desirable to greatly improve the efficiency of anodic oxygen evolution and cathodic hydrogen evolution reactions. Herein, iron-nickel/carbon nanotube composites are synthesized as efficient bifunctional electrocatalysts for water splitting. The catalyst is homogeneously distributed, while the formation of iron-nickel alloy is confirmed. Because of the synergism of iron and copper and the contribution of carbon nanotubes, the Fe–Ni/CNT electrocatalyst shows excellent oxygen evolution reaction performance with the overpotential of 221 mV at 10 mA cm^?2 and maintains stable at 0.48 V for 150 h. It expedites overall water splitting at 10 mA cm^?2 with 1.50 V and show excellent stability at 20 mA cm^?2 for 65 h, providing great potential for large-scale applications.     

Bifunctional nanoporous ruthenium-nickel alloy nanowire electrocatalysts towards oxygen/hydrogen evolution reaction

A class of ruthenium-nickel alloy catalysts featured with nanoporous nanowires (NPNWs) were synthesized by a strategy combining rapid solidification with two-step dealloying. RuNi NPNWs exhibit excellent electrocatalytic activity and stability for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in which the RuNi-2500 NPNWs catalyst shows an OER overpotential of 327 mV to deliver a current density of 10 mA cm^?2 and the RuNi-0 NPNWs catalyst requires the overpotential of 69 mV at 10 mA cm^?2 showing the best HER activity in alkaline media. Moreover, the RuNi-1500 NPNWs catalyst was used as the bifunctional electrocatalyst in a two-electrode alkaline electrolyzer for water splitting, which exhibits a low cell voltage of 1.553 V and a long-term stability of 24 h at 10 mA cm^?2, demonstrating that the RuNi NPNWs catalysts can be considered as promising bifunctional alkaline electrocatalysts.     

Directly application of bimetallic 2D-MOF for advanced electrocatalytic oxygen evolution

The development of non-noble oxygen evolution reaction (OER) catalysts with low energy consumption and cost is imperative to produce hydrogen energy from water splitting and enlarge its application. Two-dimensional (2D) metal organic frameworks (MOF) and their derivatives are widely regarded as promising electrocatalysts (EC) for OER due to its unique structural characteristics. Here, by optimizing the molar ratio of Ni to Co, bimetal 2-methylimidazole based 2D-MOF is synthesized and its derivatives are also obtained by phosphorization or oxidation. OER measurements prove that the original MOF structure with 5% Ni/Co molar ratio shows excellent activity with 310 mV overpotential (?) at the current density of 10 mA cm^?2 in 1 M KOH solution for OER, as well as a fairly good electrochemical stability rather than their oxidation or phosphorus derivatives. This work introduces a facile method to prepare bimetal imidazole-based 2D-MOF directly applied in energy conversion field without transformation, making a contribution for opening a new window of widely application of 2D-MOF and improving the hydrogen production efficiency from water splitting.     

High throughput preparation of Ni–Mo alloy thin films as efficient bifunctional electrocatalysts for water splitting

The synthesis of cost-effective and high-performance electrocatalysts for water splitting is the main challenge in electrochemical hydrogen production. In this study, we adopted a high throughput method to prepare bi-metallic catalysts for oxygen/hydrogen evolution reactions (OER/HER). A series of Ni–Mo alloy electrocatalysts with tunable compositions were prepared by a simple co-sputtering method. Due to the synergistic effect between Ni and Mo, the intrinsic electrocatalytic activity of the Ni–Mo alloy electrocatalysts is improved, resulting in excellent HER and OER performances. The Ni₉₀Mo₁₀ electrocatalyst shows the best HER performance, with an extremely low overpotential of 58 mV at 10 mA cm^?2, while the Ni₄₀Mo₆₀ electrocatalyst shows an overpotential of 258 mV at 10 mA cm^?2 in OER. More significantly, the assembled Ni₄₀Mo₆₀//Ni₉₀Mo₁₀ electrolyzer only needs a cell voltage of 1.57 V to reach 10 mA cm^?2 for overall water splitting.     

In situ assembly of ultrafine AuPd nanowires as efficient electrocatalysts for ethanol electroxidation

Improving the catalytic activity and durability of the ethanol oxidation reaction (EOR) is crucial for realizing the commercialization of direct ethanol fuel cells (DEFCs). Herein, we design a facile route to fabricate AuPd nanowires as highly efficient electrocatalysts toward ethanol oxidation reaction (EOR), where AuPd nanowires were in-situ assembled through the co-reduction of HAuCl₄ and PdCl₂ in aqueous solution in the presence of Triton X-114 and with potassium borohydride as the reducing reagent. The surface microstructure and composition of AuPd alloyed nanowires with the diameter of 4 nm were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and high resolution-transmission electron microscopy (HR-TEM). Among the AuPd NWs series, Au₈Pd₃ NWs demonstrated the best electrocatalytic activity (mass activity 10,570 mA mg^?1_Pd) and enhanced durability for ethanol electroxidation (retained 54% after 300 cycles) among the samples. The enhanced activities in EOR can be ascribed to the synergic electronic and structural effects of AuPd NWs. This work can provide a feasible method to boost Pd-alloy based electrocatalysts for EOR in direct ethanol fuel cells.