Carbon Nanotubes Decorated with CoP Nanocrystals: A Highly Active Non‐Noble‐Metal Nanohybrid Electrocatalyst for Hydrogen Evolution

The development of effective and inexpensive hydrogen evolution reaction (HER) electrocatalysts for future renewable energy systems is highly desired. The strongly acidic conditions in proton exchange membranes create a need for acid‐stable HER catalysts. A nanohybrid that consists of carbon nanotubes decorated with CoP nanocrystals (CoP/CNT) was prepared by the low‐temperature phosphidation of a Co₃O₄/CNT precursor. As a novel non‐noble‐metal HER catalyst operating in acidic electrolytes, the nanohybrid exhibits an onset overpotential of as low as 40 mV, a Tafel slope of 54 mV dec^?1, an exchange current density of 0.13 mA cm^?2, and a Faradaic efficiency of nearly 100 %. This catalyst maintains its catalytic activity for at least 18 hours and only requires overpotentials of 70 and 122 mV to attain current densities of 2 and 10 mA cm^?2, respectively.     

Iron Porphyrin Allows Fast and Selective Electrocatalytic Conversion of CO2 to CO in a Flow Cell

Molecular catalysts have been shown to have high selectivity for CO₂ electrochemical reduction to CO, but with current densities significantly below those obtained with solid-state materials. By depositing a simple Fe porphyrin mixed with carbon black onto a carbon paper support, it was possible to obtain a catalytic material that could be used in a flow cell for fast and selective conversion of CO₂ to CO. At neutral pH (7.3) a current density as high as 83.7 mA cm⁻² was obtained with a CO selectivity close to 98 %. In basic solution (pH 14), a current density of 27 mA cm⁻² was maintained for 24 h with 99.7 % selectivity for CO at only 50 mV overpotential, leading to a record energy efficiency of 71 %. In addition, a current density for CO production as high as 152 mA cm⁻² (>98 % selectivity) was obtained at a low overpotential of 470 mV, outperforming state-of-the-art noble metal based catalysts.     

Regulation of Coordination Number over Single Co Sites: Triggering the Efficient Electroreduction of CO2

The design of active, selective, and stable CO₂ reduction electrocatalysts is still challenging. A series of atomically dispersed Co catalysts with different nitrogen coordination numbers were prepared and their CO₂ electroreduction catalytic performance was explored. The best catalyst, atomically dispersed Co with two‐coordinate nitrogen atoms, achieves both high selectivity and superior activity with 94 % CO formation Faradaic efficiency and a current density of 18.1 mA cm^?2 at an overpotential of 520 mV. The CO formation turnover frequency reaches a record value of 18 200 h^?1, surpassing most reported metal‐based catalysts under comparable conditions. Our experimental and theoretical results demonstrate that lower a coordination number facilitates activation of CO₂ to the CO₂^.? intermediate and hence enhances CO₂ electroreduction activity.     

Heterostructured Inter‐Doped Ruthenium–Cobalt Oxide Hollow Nanosheet Arrays for Highly Efficient Overall Water Splitting

The development of transition‐metal‐oxides (TMOs)‐based bifunctional catalysts toward efficient overall water splitting through delicate control of composition and structure is a challenging task. Herein, the rational design and controllable fabrication of unique heterostructured inter‐doped ruthenium–cobalt oxide [(Ru–Co)O_x] hollow nanosheet arrays on carbon cloth is reported. Benefiting from the desirable compositional and structural advantages of more exposed active sites, optimized electronic structure, and interfacial synergy effect, the (Ru–Co)O_x nanoarrays exhibited outstanding performance as a bifunctional catalyst. Particularly, the catalyst showed a remarkable hydrogen evolution reaction (HER) activity with an overpotential of 44.1 mV at 10 mA cm^?2 and a small Tafel slope of 23.5 mV dec^?1, as well as an excellent oxygen evolution reaction (OER) activity with an overpotential of 171.2 mV at 10 mA cm^?2. As a result, a very low cell voltage of 1.488 V was needed at 10 mA cm^?2 for alkaline overall water splitting.     

Two‐Dimensional Co@N‐Carbon Nanocomposites Facilely Derived from Metal–Organic Framework Nanosheets for Efficient Bifunctional Electrocatalysis

Metal–organic frameworks (MOFs) and MOF‐derived nanomaterials have recently attracted great interest as highly efficient, non‐noble‐metal catalysts. In particular, two‐dimensional MOF nanosheet materials possess the advantages of both 2D layered nanomaterials and MOFs and are considered to be promising nanomaterials. Herein, we report a facile and scalable in situ hydrothermal synthesis of Co–hypoxanthine (HPA) MOF nanosheets, which were then directly carbonized to prepare uniform Co@N‐Carbon nanosheets for efficient bifunctional electrocatalytic hydrogen‐evolution reactions (HERs) and oxygen‐evolution reactions (OERs). The Co embedded in N‐doped carbon shows excellent and stable catalytic performance for bifunctional electrocatalytic OERs and HERs. For OERs, the overpotential of Co@N‐Carbon at 10 mA cm^?2 was 400 mV (vs. reversible hydrogen electrode, RHE). The current density of Co@N‐Carbon reached 100 mA cm^?2 at an overpotential of 560 mV, which showed much better performance than RuO₂; the largest current density of RuO₂ that could be reached was only 44 mA cm^?2. The Tafel slope of Co@N‐Carbon was 61 mV dec^?1, which is comparable to that of commercial RuO₂ (58 mV dec^?1). The excellent electrocatalytic properties can be attributed to the nanosheet structure and well‐dispersed carbon‐encapsulated Co, CoN nanoparticles, and N‐dopant sites, which provided high conductivity and a large number of accessible active sites. The results highlight the great potential of utilizing MOF nanosheet materials as promising templates for the preparation of 2D Co@N‐Carbon materials for electrocatalysis and will pave the way to the development of more efficient 2D nanomaterials for various catalytic applications.     

Non‐3d Metal Modulation of a Cobalt Imidazolate Framework for Excellent Electrocatalytic Oxygen Evolution in Neutral Media

Cobalt imidazolate frameworks are classical electrocatalysts for the oxygen evolution reaction (OER) but suffer from the relatively low activity. Here, a non‐3d metal modulation strategy is presented for enhancing the OER activity of cobalt imidazolate frameworks. Two isomorphous frameworks [Co₄(MO₄)(eim)₆] (M=Mo or W, Heim=2‐ethylimidazole) having Co(eim)₃(MO₄) units and high water stabilities were designed and synthesized. In different neutral media, the Mo‐modulated framework coated on a glassy carbon electrode shows the best OER performances (1 mA cm^?2 at an overpotential of 210 mV in CO₂‐saturated 0.5 m KHCO₃ electrolyte and 2/10/22 mA cm^?2 at overpotential of 388/490/570 mV in phosphate buffer solution) among non‐precious metal catalysts and even outperforms RuO₂. Spectroscopic measurements and computational simulations revealed that the non‐3d metals modulate the electronic structure of Co for optimum reactant/product adsorption and tailor the energy of rate‐determining step to a more moderate value.     

Imine Gels Based on Ferrocene and Porphyrin and Their Electrocatalytic Property

A series of porphyrin‐based imine gels have been synthesized via dynamic covalent gelation between 5,10,15,20‐tetra(4‐aminophenyl)‐21H,23H‐porphyrin (H₂TAPP) derivatives and various aldehyde compounds. The porphyrin‐ferrocene imine gels based on MTAPP (M=H₂, Ni²⁺, Co²⁺, Pd²⁺ and Zn²⁺) and ferrocene‐1,1′‐dicarbaldehyde (NA) display efficient HER, OER and ORR activities in alkaline media. Among the gels, CoTAPP‐NA shows an HER current density of 10 mA cm^?2 at low overpotential of 470 mV and small Tafel slope of 110 mV decade^?1 in alkaline media. CoTAPP‐NA also exhibits OER catalytic activity with low overpotential (416 mV for 10 mA cm^?2). CoTAPP‐NA shows ability in overall water splitting in alkaline media. In addition, CoTAPP‐NA exhibits onset potential (E_p) of 0.95 V and half‐wave potential (E_1/2) of 0.84 V in 1.0 mol L^?1 KOH solution for oxygen reduction. Moreover, the gel catalyst shows good stability.     

Synthesis of Tri‐functional Core‐shell CuO@carbon Quantum Dots@carbon Hollow Nanospheres Heterostructure for Non‐enzymatic H2O2 Sensing and Overall Water Splitting Applications

A core‐shell structure with CuO core and carbon quantum dots (CQDs) and carbon hollow nanospheres (CHNS) shell was prepared through facile in‐situ hydrothermal process. The composite was used for non‐enzymatic hydrogen peroxide sensing and electrochemical overall water splitting. The core‐shell structure was established from the transmission electron microscopy image analysis. Raman and UV‐Vis spectroscopy analysis confirmed the interaction between CuO and CQDs. The electrochemical studies showed the limit of detection and sensitivity of the prepared composite as 2.4 nM and 56.72 μA μM^?1 cm^?2, respectively. The core‐shell structure facilitated better charge transportation which in turn exhibited elevated electro‐catalysis towards hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and overall water splitting. The overpotential of 159 mV was required to achieve 10 mA cm^?2 current density for HER and an overpotential of 322 mV was required to achieve 10 mA cm^?2 current density for OER in 1.0 M KOH. A two‐electrode system was constructed for overall water splitting reaction, which showed 10 and 50 mA cm^?2 current density at 1.83 and 1.96 V, respectively. The prepared CuO@CQDs@CHNS catalyst demonstrated excellent robustness in HER and OER catalyzing condition along with overall water splitting reaction. Therefore, the CuO@CQDs@CHNS could be considered as promising electro‐catalyst for H₂O₂ sensing, HER, OER and overall water splitting.     

Graphitic Carbon Nitride Nanoribbons: Graphene‐Assisted Formation and Synergic Function for Highly Efficient Hydrogen Evolution

The development of new promising metal‐free catalysts is of great significance for the electrocatalytic hydrogen evolution reaction (HER). Herein, a rationally assembled three‐dimensional (3D) architecture of 1D graphitic carbon nitride (g‐C₃N₄) nanoribbons with 2D graphene sheets has been developed by a one‐step hydrothermal method. Because of the multipathway of charge and mass transport, the hierarchically structured g‐C₃N₄ nanoribbon–graphene hybrids lead to a high electrocatalytic ability for HER with a Tafel slope of 54 mV decade^?1, a low onset overpotential of 80 mV and overpotential of 207 mV to approach a current of 10 mA cm^?2, superior to those non‐metal materials and well‐developed metallic catalysts reported previously. This work presents a great advance for designing and developing highly efficient metal‐free catalyst for hydrogen evolution.     

Water Oxidation Catalysis Beginning with CuCo2S4: Investigation of the True Electrochemically Driven Catalyst

The exploitation of efficient and stable water oxidation catalysts is a pressing challenge to solve the energy crisis. Herein, flower‐like CuCo₂S₄ microspheres were successfully synthesized and used as an effective water oxidation catalyst. CuCo₂S₄/NF (NF=nickel foam) affords electrocatalytic water oxidation activity, with a current density of 20 mA cm^?2 at a low overpotential of 260 mV. The overpotential value is lower than that of benchmark RuO₂/NF (overpotential of 340 mV at a current density of 20 mA cm^?2). The water oxidation activity increases linearly before nonlinearly improving with increasing pH; this indicates that the substrate changes from water to hydroxyl. The CuCo₂S₄/NF catalyst is demonstrated to be a real water oxidation catalyst based on diverse experiments.     

Bifunctional Electrocatalysts for Overall Water Splitting from an Iron/Nickel‐Based Bimetallic Metal–Organic Framework/Dicyandiamide Composite

Pyrolysis of a bimetallic metal–organic framework (MIL‐88‐Fe/Ni)‐dicyandiamide composite yield a Fe and Ni containing carbonaceous material, which is an efficient bifunctional electrocatalyst for overall water splitting. FeNi₃ and NiFe₂O₄ are found as metallic and metal oxide compounds closely embedded in an N‐doped carbon–carbon nanotube matrix. This hybrid catalyst (Fe‐Ni@NC‐CNTs) significantly promotes the charge transfer efficiency and restrains the corrosion of the metallic catalysts, which is shown in a high OER and HER activity with an overpotential of 274 and 202 mV, respectively at 10 mA cm^?2 in alkaline solution. When this bifunctional catalyst was further used for H₂ and O₂ production in an electrochemical water‐splitting unit, it can operate in ambient conditions with a competitive gas production rate of 1.15 and 0.57 μL s^?1 for hydrogen and oxygen, respectively, showing its potential for practical applications.     

Selective and Efficient Reduction of Carbon Dioxide to Carbon Monoxide on Oxide‐Derived Nanostructured Silver Electrocatalysts

In this work, the selective electrocatalytic reduction of carbon dioxide to carbon monoxide on oxide‐derived silver electrocatalysts is presented. By a simple synthesis technique, the overall high faradaic efficiency for CO production on the oxide‐derived Ag was shifted by more than 400 mV towards a lower overpotential compared to that of untreated Ag. Notably, the Ag resulting from Ag oxide is capable of electrochemically reducing CO₂ to CO with approximately 80 % catalytic selectivity at a moderate overpotential of 0.49 V, which is much higher than that (ca. 4 %) of untreated Ag under identical conditions. Electrokinetic studies show that the improved catalytic activity is ascribed to the enhanced stabilization of COOH^. intermediate. Furthermore, highly nanostructured Ag is likely able to create a high local pH near the catalyst surface, which may also facilitate the catalytic activity for the reduction of CO₂ with suppressed H₂ evolution.     

An Efficient RuTe2/Graphene Catalyst for Electrochemical Hydrogen Evolution Reaction in Acid Electrolyte

Developing efficient powder catalysts for hydrogen evolution reaction (HER) in the acidic electrolyte is significant for hydrogen generation in the proton exchange membrane (PEM) water electrolysis technique. Herein, we demonstrated an efficient catalyst for HER in the acid media based on the graphene supported ruthenium telluride nanoparticles (RuTe₂/Gr). The catalysts were easily fabricated by a facile microwave irradiation/thermal annealing approach, and orthorhombic RuTe₂ crystals were found anchored over the graphene surface. The defective structure was demonstrated in the aberration‐corrected transmission electron microscopy images for RuTe₂ crystals and graphene support. This catalyst required an overpotential of 72 mV to drive 10 mA cm^?2 for HER when loading on the inert glass carbon electrode; Excellent catalytic stability in acidic media was also observed to offer 10 mA cm^?2 for 10 hours. The Volmer‐Tafel mechanism was indicated on RuTe₂/Gr catalyst by Tafel slope of 33 mV dec^?1, similar to that of Pt/C catalysts. The high catalytic performance of RuTe₂/Gr could be attributed to its high dispersion on the graphene surface, high electrical conductivity and low charge transfer resistance. This powder catalyst has potential application in the PEM water electrolysis technique because of its low cost and high stability.     

Electrodeposited Amorphous Tungsten‐doped Cobalt Oxide as an Efficient Catalyst for the Oxygen Evolution Reaction

Thin film of amorphous tungsten‐doped cobalt oxide (W:CoO) was successfully grown on a conducting electrode via an electrochemical oxidation process employing a [Co(WS₄)₂]^2? deposition bath. The W:CoO catalyst displays an attractive performance for the oxygen evolution reaction in an alkaline solution. In an NaOH solution of pH 13, W:CoO operates with a moderate onset overpotential of 230 mV and requires 320 mV overpotential to generate a catalytic current density of 10 mA cm^?2. A low Tafel slope of 45 mV decade^?1 was determined, indicating a rapid O₂‐evolving kinetics. The as‐prepared W:CoO belongs to the best cobalt oxide‐based catalysts ever reported for the oxygen evolution (OER) reaction.     

Iridium‐Based Cubic Nanocages with 1.1‐nm‐Thick Walls: A Highly Efficient and Durable Electrocatalyst for Water Oxidation in an Acidic Medium

We report a highly active and durable water oxidation electrocatalyst based on cubic nanocages with a composition of Ir₄₄Pd₁₀, together with well‐defined {100} facets and porous walls of roughly 1.1 nm in thickness. Such nanocages substantially outperform all the water oxidation electrocatalysts reported in literature, with an overpotential of only 226 mV for reaching 10 mA cm^?2_geo at a loading of Ir as low as 12.5 μg_Ir cm^?2 on the electrode in acidic media. When benchmarked against a commercial Ir/C electrocatalyst at 250 mV of overpotential, such a nanocage‐based catalyst not only shows enhancements (18.1‐ and 26.2‐fold, respectively) in terms of mass (1.99 A mg^?1_Ir) and specific (3.93 mA cm^?2_Ir) activities, but also greatly enhanced durability. The enhancements can be attributed to a combination of multiple merits, including a high utilization efficiency of Ir atoms and an open structure beneficial to the electrochemical oxidation of Ir to the active form of IrO_x.     

Boosting Electrochemical Reduction of CO2 at a Low Overpotential by Amorphous Ag‐Bi‐S‐O Decorated Bi0 Nanocrystals

Bimetal‐S‐O composites have been rarely researched in electrochemical reduction of CO₂. Now, an amorphous Ag‐Bi‐S‐O decorated Bi⁰ catalyst derived from Ag_0.95BiS_0.75O_3.1 nanorods by electrochemical pre‐treatment was used for catalyzing eCO₂RR, which exhibited a formate FE of 94.3 % with a formate partial current density of 12.52 mA cm^?2 at an overpotential of only 450 mV. This superior performance was attributed to the attached amorphous Ag‐Bi‐S‐O substance. S could be retained in the amorphous region after electrochemical pre‐treatment only in samples derived from metal‐S‐O composites, and it would greatly enhance the formate selectivity by accelerating the dissociation of H₂O. The existence of Ag would increase the current density, resulting in a higher local pH, which made the role of S in activating H₂O more significantly and suppressed H₂ evolution more effectively, thus endowing the catalyst with a higher formate FE at low overpotentials.     

Covalently Grafting Cobalt Porphyrin onto Carbon Nanotubes for Efficient CO2 Electroreduction

Molecular complexes with inexpensive transition‐metal centers have drawn extensive attention, as they show a high selectivity in the electrochemical conversion of CO₂ to CO. In this work, we propose a new strategy to covalently graft cobalt porphyrin onto the surface of a carbon nanotube by a substitution reaction at the metal center. Material characterization and electrochemical studies reveal that the porphyrin molecules are well dispersed at a high loading of 10 wt. %. As a result, the turnover frequency for CO formation is improved by a factor of three compared to traditional physically‐mixed catalysts with the same cobalt content. This leads to an outstanding overall current density of 25.1 mA cm^?2 and a Faradaic efficiency of 98.3 % at 490 mV overpotential with excellent long‐term stability. This work provides an effective pathway for the improvement of the performance of electrocatalysts that could inspire rational design of molecular catalysts in the future.     

Controlled Synthesis of 3D Flower‐like Ni2P Composed of Mesoporous Nanoplates for Overall Water Splitting

Developing efficient non‐noble metal and earth‐abundant electrocatalysts with tunable microstructures for overall water splitting is critical to promote clean energy technologies for a hydrogen economy. Herein, novel three‐dimensional (3D) flower‐like Ni₂P composed of mesoporous nanoplates with controllable morphology and high surface area was prepared by a hydrothermal method and low‐temperature phosphidation as efficient electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Compared with the urchin‐like Ni_x P_y , the 3D flower‐like Ni₂P with a diameter of 5 μm presented an efficient and stable catalytic performance in 0.5 m H₂SO₄, with a small Tafel slope of 79 mV dec⁻¹ and an overpotential of about 240 mV at a current density of 10 mA cm⁻² with a mass loading density of 0.283 mg cm⁻². In addition, the catalyst also exhibited a remarkable performance for the OER in 1.0 m KOH electrolyte, with an overpotential of 320 mV to reach a current density of 10 mA cm⁻² and a small Tafel slope of 72 mV dec⁻¹. The excellent catalytic performance of the as‐prepared Ni₂P may be ascribed to its novel 3D morphology with unique mesoporous structure.     

Regulating the Spin State of FeIII by Atomically Anchoring on Ultrathin Titanium Dioxide for Efficient Oxygen Evolution Electrocatalysis

Ferric oxides and (oxy)hydroxides, although plentiful and low‐cost, are rarely considered for oxygen evolution reaction (OER) owing to the too high spin state (e_g filling ca. 2.0) suppressing the bonding strength with reaction intermediates. Now, a facile adsorption–oxidation strategy is used to anchor Fe^III atomically on an ultrathin TiO₂ nanobelt to synergistically lower the spin state (e_g filling ca. 1.08) to enhance the adsorption with oxygen‐containing intermediates and improve the electro‐conductibility for lower ohmic loss. The electronic structure of the catalyst is predicted by DFT calculation and perfectly confirmed by experimental results. The catalyst exhibits superior performance for OER with overpotential 270 mV @10 mA cm^?2 and 376 mV @100 mA cm^?2 in alkaline solution, which is much better than IrO₂/C and RuO₂/C and is the best iron‐based OER catalyst free of active metals such as Ni, Co, or precious metals.     

Molybdenum‐tungsten Oxide Nanowires Rich in Oxygen Vacancies as An Advanced Electrocatalyst for Hydrogen Evolution

Electrolysis of water is a promising way to produce hydrogen fuel in large scale. The commercialization of this technology requires highly efficient non‐noble metal electrocatalysts to decease the energy input for the hydrogen evolution reaction (HER). In this work, a novel nanowire structured molybdenum‐tungsten bimetallic oxide (CTAB‐D‐W₄MoO₃) is synthesized by a simple hydrothermal method followed with post annealing treatment. The obtained metal oxides feature with enhanced conductivity, rich oxygen vacancies and customized electronic structure. As such, the composite electrocatalyst exhibits excellent electrocatalytic performance for HER in an acidic environment, achieving a large current density of 100 mA cm^?2 at overpotential of only 286 mV and a small Tafel slope of 71.2 mV dec^?1. The excellent electrocatalytic HER performance of CTAB‐D‐W₄MoO₃ is attributed to the unique nanowire structure, rich catalytic active sites and promoted electron transfer rate.