Dual-site catalysts featuring platinum-group-metal atoms on copper shapes boost hydrocarbon formations in electrocatalytic CO2 reduction.

Copper-based catalyst is uniquely positioned to catalyze the hydrocarbon formations through electrochemical CO2 reduction. The catalyst design freedom is limited for alloying copper with H-affinitive elements represented by platinum group metals because the latter would easily drive the hydrogen evolution reaction to override CO2 reduction. We report an adept design of anchoring atomically dispersed platinum group metal species on both polycrystalline and shape-controlled Cu catalysts, which now promote targeted CO2 reduction reaction while frustrating the undesired hydrogen evolution reaction. Notably, alloys with similar metal formulations but comprising small platinum or palladium clusters would fail this objective. With an appreciable amount of CO-Pd1 moieties on copper surfaces, facile CO* hydrogenation to CHO* or CO-CHO* coupling is now viable as one of the main pathways on Cu(111) or Cu(100) to selectively produce CH4 or C2H4 through Pd-Cu dual-site pathways. The work broadens copper alloying choices for CO2 reduction in aqueous phases.

Photoelectrochemical OER activity by employing BiVO4 with manganese oxide co-catalysts.

The structure-activity relationship in the electrochemical OER has been studied widely, but aspects of the photoelectrochemical (PEC) O2 evolution activity with different manganese oxides are not fully explored. In the present study different manganese oxides (MnO2, MnOx (a mixture of Mn3+ and Mn4+ ions), Mn2O3, and Mn3O4) have been electrodeposited onto the BiVO4 photoanode as co-catalysts for PEC water splitting. We find that BiVO4-MnOx shows the lowest onset potential of 0.33 V vs. RHE and the highest activity among the manganese oxides. Annealing at different temperatures results in the improvement of the OER kinetics at the interface with some detrimental effect on the activity of BiVO4. Such a study may lead to useful changes in the fabrication of semiconductor thin film photoelectrodes useful for PEC water splitting.

Covalently Linked Heterostructures of Phosphorene with MoS2/MoSe2 and Their Remarkable Hydrogen Evolution Reaction Activity.

Hydrogen production by photochemical and electrochemical means is an important area of research related to renewable energy. 2D nanomaterials such as C3N4 and MoS2 have proven to be active for the hydrogen evolution reaction (HER). Phosphorene, a mono-elemental 2D layer of phosphorus, is known to catalyze the HER, but the activity is marginal. The use of phosphorene is also limited by its ambient instability. We have been able to prepare covalently cross-linked nanocomposites of phosphorene with MoS2 as well as MoSe2. The phosphorene-MoS2 nanocomposite shows excellent photochemical HER activity yielding 26.8 mmol h-1 g-1 of H2, while only a negligible amount is produced by the physical mixture of phosphorene and MoS2. The phosphorene-MoS2 composite also displays high electrochemical HER activity with an onset overpotential of 110 mV, close to that of Pt. The enhanced HER activity of the phosphorene-MoS2 nanocomposite can be attributed to the ordered cross-linking of the 2D sheets, increasing the interfacial area as well as the charge-transfer interaction between phosphorene and MoS2 layers. The phosphorene-MoSe2 nanocomposite also exhibits good photochemical HER activity.

Borocarbonitrides as Metal-Free Catalysts for the Hydrogen Evolution Reaction.

Hydrogen generation by water splitting is clearly a predominant and essential strategy to tackle the problems related to renewable energy. In this context, the discovery of proper catalysts for electrochemical and photochemical water splitting assumes great importance. There is also a serious intent to eliminate platinum and other noble metal catalysts. To replace Pt by a non-metallic catalyst with desirable characteristics is a challenge. Borocarbonitrides, (Bx Cy Nz ) which constitutes a new class of 2D material, offer great promise as non-metallic catalysts because of the easy tunability of bandgap, surface area, and other electronic properties with variation in composition. Recently, Bx Cy Nz composites with excellent electrochemical and photochemical hydrogen generation activities have been found, especially noteworthy being the observation that Bx Cy Nz with a carbon-rich composition or its nanocomposites with MoS2 come close to Pt in electrocatalytic properties, showing equally good photochemical activity.

Photochemical and Photoelectrochemical Hydrogen Generation by Splitting Seawater.

Producing hydrogen from water in an efficient manner could significantly reduce consumption of fossil fuels. In this regard the abundant presence of water in oceans offers an important alternative approach for water splitting using seawater. Direct use of seawater for the generation of hydrogen is a difficult and complex process due to the presence of various ions in seawater, which affect the activity of the catalysts and makes the selectivity towards efficient water splitting a challenging task. Herein various ways are reported to efficiently reduce seawater to hydrogen under visible light irradiation by various catalysts already reported by this group. A better performance than pure water was observed in some cases, and in a few cases the opposite was observed, implying that with a proper approach seawater can be efficiently reduced to generate hydrogen.

Photoelectrochemical hydrogen generation employing a Cu2O-based photocathode with improved stability and activity by using NixPy as the cocatalyst.

With the tactical integration of band edge energetics concepts in semiconducting films to reduce charge recombination and photocorrosion, an improvement in the photocurrent can be achieved by introducing CuO and NixPy into Cu2O films. Photodegradation limitations of Cu2O are overcome by the Cu2O-CuO-NixPy photocathode. NixPy, because of its excellent electrocatalytic hydrogen evolution activity, helps in obtaining better stability and activity. The individual effects of CuO and NixPy have been investigated and it is found that the activity enhancement stems mainly from the contribution of NixPy, whereas CuO helps with the unidirectional flow of photogenerated charges to prevent the photocorrosion of Cu2O. Relative to bare and modified Cu2O, Cu2O-CuO-NixPy shows a considerable reduction in the overpotential and a remarkable improvement in the photocurrent at 0 V (vs. RHE). This is the first report on the use of NixPy as the co-catalyst in a Cu2O based photocathode system to improve its photostability as well as its activity.

Unique Features of the Photocatalytic Reduction of H2O and CO2 by New Catalysts Based on the Analogues of CdS, Cd4P2X3 (X = Cl, Br, I).

Photochemical reduction of H2O and CO2 has been investigated with a new family of catalysts of the formula Cd4P2X3 (X= Cl, Br, I), obtained by the complete aliovalent substitution of the sulfide ions in CdS by P and X (Cl, Br, I). Unlike CdS, the Cd4P2X3 compounds exhibit hydrogen evolution and CO2 reduction from water even in the absence of a sacrificial agent or a cocatalyst. Use of NixPy as the cocatalyst, enhances hydrogen evolution, reaching 3870 (apparent quantum yield (AQY) = 4.11) and 9258 (AQY = 9.83) µmol h-1 g-1, respectively, under artificial and natural (sunlight) irradiation, in the case of Cd4P2Br3/NixPy. Electrochemical and spectroscopic studies have been employed to understand the photocatalytic activity of this family of compounds. Unlike most of the semiconductor-based photocatalysts, Cd4P2X3 catalysts reduce CO2 to CO and CH4 in the absence of sacrificial-agent or cocatalyst using water as the electron source. CO, CH4, and H2 have been obtained with these catalysts under artificial as well as sun-light irradiation. First-principles, calculations have been carried out to understand the electronic structure and catalytic features of these new catalysts.

Electrocatalytic hydrogen evolution reaction activity comparable to platinum exhibited by the Ni/Ni(OH)2/graphite electrode.

Electrochemical dual-pulse plating with sequential galvanostatic and potentiostatic pulses has been used to fabricate an electrocatalytically active Ni/Ni(OH)2/graphite electrode. This electrode design strategy to generate the Ni/Ni(OH)2 interface on graphite from Ni deposits is promising for electrochemical applications and has been used by us for hydrogen generation. The synergetic effect of nickel, colloidal nickel hydroxide islands, and the enhanced surface area of the graphite substrate facilitating HO-H cleavage followed by H(ad) recombination, results in the high current density [200 mA/cm2 at an overpotential of 0.3 V comparable to platinum (0.44 V)]. The easy method of fabrication of the electrode, which is also inexpensive, prompts us to explore its use in fabrication of solar-driven electrolysis.

Pd-Pt alloys nanowires as support-less electrocatalyst with high synergistic enhancement in efficiency for methanol oxidation in acidic medium.

In a facile approach, Pd73Pt27 alloy nanowires (NWs) with large aspect ratios were synthesized in high yield by using sacrificial templates. Unlike majority of processes, our synthesis was carried out in aqueous solution with no intermittent separating stages for the products, while maintaining the NW morphology up to ∼30% of Pt. Upon evaporation of their dispersion, the NWs transform into a stable porous membrane due to self-entanglement and can be directly lifted and employed for electrocatalytic applications without external catalyst supports. We show that the NW membranes exhibit efficient electrocatalytic performance for methanol oxidation reaction (MOR) with 10 times higher mass activity and 4.4 times higher specific activity in acidic media as compared to commercial Pt catalysts. The membrane electrocatalysts is robust and exhibited very good stability with retention of ∼70% mass-activity after 4000 potential cycles. Since Pd was found to be inert towards MOR in acidic medium, our investigation provides a direct estimate of synergistic enhancement of efficiency. Over 10 times increment of mass activity appears to be significantly higher than previous investigations in various other reaction media.

Beneficial effect of Re doping on the electrochemical HER activity of MoS2 fullerenes.

Electrochemical generation of hydrogen by non-precious metal electrocatalysts at a lower overpotential is a focus area of research directed towards sustainable energy. The exorbitant costs associated with Pt-based catalysts is the major bottleneck associated with commercial-scale hydrogen generation. Strategies for the synthesis of cost-effective and stable catalysts are thus key for a prospective 'hydrogen economy'. In this report, we highlight a novel and general strategy to enhance the electrochemical activity of molybdenum disulfide (MoS2) in a fullerene structure (IF-). In particular, pristine (undoped) and rhenium-doped nanoparticles of MoS2 with fullerene-like structures (IF-MoS2) were studied, and their performance as catalysts for the hydrogen evolution reaction (HER) was compared to that of 2H-MoS2 particles (platelets). The current density of the IF-MoS2 was higher by one order of magnitude than that of few-layer (FL-) MoS2, due to the enhanced density of the edge sites. Furthermore, Re doping of as low as 100 ppm in IF-MoS2 decreased the onset potential by 60-80 mV and increased the activity by 60 times compared with that of the FL-MoS2. The combined synergistic effect of Re doping and the IF structure not only changes the intrinsic nature of the MoS2 but also increases its reactivity. This strategy highlights the potential use of the IF structure and Re doping in electrocatalytic hydrogen evolution using MoS2-based catalysts.

Mechanochemical Synthesis of Free-Standing Platinum Nanosheets and Their Electrocatalytic Properties.

Robust, 26 nm thick free-standing platinum nanosheets, an extremely rare morphology for metal nanostructures, are obtained by employing fluid induced shearing force of the order of 1.8 N and differential shear-stress of 0.5 kPa across the diameter of a Te template nanorod undergoing galvanic displacement by Pt4+ . Corrugation leads to their large surface area and much improved electrocatalytic properties when compared with conventional Pt catalysts.

High-yield synthesis of sub-10 nm Pt nanotetrahedra with bare ⟨111⟩ facets for efficient electrocatalytic applications.

Unlike other shapes, the design of tetrahedral Pt nanocrystals (Pt-NTd), which have the largest number of Pt(111) surface atoms and highest catalytic activities toward the electron transfer reactions, has widely been considered a synthetic challenge due to their thermodynamic instability. Here, we show that, by inducing their nucleation on functionalized carbon, Pt NTds can be obtained with tunable sizes and high yields. The carbon support anchors the nanocrystals early and prevents their oriented attachment leading to nanowire formation. Therein, an in situ generated amine is crucial for stabilization of Pt-NTds, which can later be removed to expose the Pt(111) facets for higher catalytic efficiency. The bare nanocrystals exhibit much improved stability and electrocatalytic activity characteristic of Pt(111) toward oxygen reduction reaction (ORR) and methanol and formic acid oxidation reactions. For example, ∼90% of their activity was retained after 5000 potential cycles, while the ORR onset potential was recorded to be very high, 1.01 V vs reversible hydrogen electrode (RHE).