Improving the Performance of Pd for Formic Acid Dehydrogenation by Introducing Barium Titanate.

Formic acid, a safe and widely available organic compound, produces hydrogen under mild conditions, with the existence of Pd-based catalysts. Efficiently generating hydrogen via formic acid decomposition (FAD) is restricted by the cleavage of the C-H bond in adsorbed HCOO* and strong adsorption of hydrogen on the Pd surface. Herein, tetragonal-phase barium titanate (TBT) was in situ grown on reduced graphene oxide (rGO) to support Pd (Pd/TBT/rGO) for FAD. The internal electric field exists around TBT owing to its spontaneous polarization capacity. The physical characterizations illustrate that the introduction of barium titanate affects the catalytic performance of the catalyst by decreasing the particle size of Pd nanoparticles (NPs) and forming electron-rich Pd. The as-synthesized Pd/TBT/rGO exhibited excellent catalytic activity and hydrogen selectivity for FAD with a high initial turnover frequency up to 3019.72 h-1 at 333 K. The reason for this enhancement is not only the small-size Pd NPs but also the internal electric field from TBT, which promotes the desorption of adsorbed hydrogen on the Pd surface. Additionally, the electron-rich Pd is favorable to the cleavage of the C-H bond in HCOO*. This work will improve the understanding of the characterization of barium titanate and provide a new design strategy for the FAD catalyst.

Carbon-coated silica supported palladium for hydrogen production from formic acid - Exploring the influence of strong metal support interaction.

Hydrogen energy is one of the most promising energy carriers to solve the increasingly severe energy crisis. Formic acid decomposition (FAD) solves the storage and transportation problems of hydrogen gas since hydrogen can be produced from aqueous formic acid under mild conditions. To efficiently convert formic acid to hydrogen gas, chemical and structural modification of Pd nanoparticles or supports have been carried out, especially introducing the strong metal support interaction (SMSI). Herein, we synthesized core-shell structured SiO2@SC compounds as the supports to introduce SMIS to Pd/PdO nanoparticles. The relationship between FAD activity and SMSI is investigated. The SMSI between Pd/PdO nanoparticles and SiO2/SC is adjusted by altering the thickness of the carbon layer. The X-ray photoelectron spectroscopy shows that owing to the strong electron-attracting ability SiO2 core contributes to leading the Pd0 active site in an electron-deficient state. The thickness of the carbon layer controls the ratio of Pd0/PdO, which enhances the anti-poisoning ability of the catalyst. Owing to the electron-deficient state of Pd0 and optimal ratio of Pd0/PdO, the hydrogen desorption rate of FAD on Pd is enhanced, and the turn over frequency of Pd/SiO2@SC-1:3 catalyst reaches 1138 h-1, which is ten times higher than that of the pristine Pd/SC catalyst. These results are believed to guide the design and development of highly active Pd-based catalysts for hydrogen generation via FAD.

Realizing anti-self-discharged lithium-sulfur batteries by using hierarchical porous carbon nanofibers embedded with Fe/Ni-N catalytic sites.

Lithium-sulfur (Li-S) batteries are featured with high gravimetric energy density, yet their commercial application is significantly deteriorated with the severe self-discharging resulted from the polysulfides shuttle and sluggish electrochemical kinetics. Here, a hierarchical porous carbon nanofibers implanted with Fe/Ni-N (denoted as Fe-Ni-HPCNF) catalytic sites are prepared and used as a kinetics booster toward anti-self-discharged Li-S batteries. In this design, the Fe-Ni-HPCNF possesses interconnected porous skeleton and abundant exposed active sites, enabling fast Li-ion conduction, excellent shuttle inhibition and catalytic ability for polysulfides' conversion. Combined with these advantages, this cell with the Fe-Ni-HPCNF equipped separator exhibits an ultralow self-discharged rate of 4.9% after resting for one week. Moreover, the modified batteries deliver a superior rate performance (783.3 mAh g-1 at 4.0 C) and an outstanding cycling life (over 700 cycles with 0.057% attenuation rate at 1.0 C). This work may guide the advanced design of anti-self-discharged Li-S batteries.

p-n heterojunction constructed by γ-Fe2O3 covering CuO with CuFe2O4 interface for visible-light-driven photoelectrochemical water oxidation.

Fe2O3 is a promising n-type semiconductor as the photoanode of photoelectrochemical water-splitting method due to its abundance, low cost, environment-friendly, and high chemical stability. However, the recombination of photogenerated holes and electrons leads to low solar-to-hydrogen efficiency. In this work, to overcome the recombination issue, a p-type semiconductor, CuO, is introduced underneath the γ-Fe2O3 to synthesize γ-Fe2O3/CuO on the FTO substrate. Along with the formation of p-n heterojunction, CuFe2O4 is in situ generated at the interface of γ-Fe2O3 and CuO. The existence of Cu2O in CuO and CuFe2O4 promotes the charge transfer from CuO to γ-Fe2O3 and within CuFe2O4, respectively, resulting in creating an internal electric field in γ-Fe2O3/CuO and leading to the conduction band of CuO bending up and γ-Fe2O3 bending down. Additionally, Cu(II) in CuFe2O4 contributes to fast electron capture. Consequently, the charge transfer efficiency and charge separation efficiency of photo-generated holes are promoted. Hence, γ-Fe2O3/CuO exhibits an enhanced photocurrent density of 13.40 mA cm-2 (1.9 times higher than γ-Fe2O3). The photo corrosion resistance of CuO is dramatically increased with the protection of CuFe2O4, resulting in superior high chemical stability, i.e. 85% of the initial activity remains after a long-term test.

Bending Resistance Covalent Organic Framework Superlattice: "Nano-Hourglass"-Induced Charge Accumulation for Flexible In-Plane Micro-Supercapacitors.

Covalent organic framework (COF) film with highly exposed active sites is considered as the promising flexible self-supported electrode for in-plane micro-supercapacitor (MSC). Superlattice configuration assembled alternately by different nanofilms based on van der Waals force can integrate the advantages of each isolated layer to exhibit unexpected performances as MSC film electrodes, which may be a novel option to ensure energy output. Herein, a mesoporous free-standing A-COF nanofilm (pore size is 3.9 nm, averaged thickness is 4.1 nm) with imine bond linkage and a microporous B-COF nanofilm (pore size is 1.5 nm, averaged thickness is 9.3 nm) with ß-keto-enamine-linkages are prepared, and for the first time, we assembly the two lattice matching films into sandwich-type superlattices via layer-by-layer transfer, in which ABA-COF superlattice stacking into a "nano-hourglass" steric configuration that can accelerate the dynamic charge transportation/accumulation and promote the sufficient redox reactions to energy storage. The fabricated flexible MSC-ABA-COF exhibits the highest intrinsic CV of 927.9 F cm-3 at 10 mV s-1 than reported two-dimensional alloy, graphite-like carbon and undoped COF-based MSC devices so far, and shows a bending-resistant energy density of 63.2 mWh cm-3 even after high-angle and repeat arbitrary bending from 0 to 180°. This work provides a feasible way to meet the demand for future miniaturization and wearable electronics.

Well-designed internal electric field from nano-ferroelectrics promotes formic acid oxidation on Pd.

Pd-Based catalysts are considered the most efficient catalysts in direct formic acid fuel cells. However, the poisoning and dissolution of Pd in acidic systems limit its commercialization. Here, we propose an all-in-one solution for the anti-dissolution and anti-poisoning properties of palladium. A novel structured catalyst, Pd nanoparticles embedded in a carbon layer internally decorated with tourmaline nanoparticles (TNPs), is proposed for formic acid oxidation (FAO). The internal electric field strength of the catalysts is readily regulated by controlling the amount of TNPs. Remarkably, the prepared catalyst exhibits as high as 3.9 times mass activity (905 A g-1) compared with the commercial Pd/C catalyst. The significant improvement in the electrocatalytic performance of the catalyst is mainly due to the polarized electric field of TNPs causing charge transfer from Pd to tourmaline, which weakens the O-H bond of HCOOH and the bond between Pd and COad. Another advantage brought by the internal polarized electric field is that it facilitates water dissociation to produce OHad, thereby improving the anti-poisoning ability of the catalyst in acidic media. Moreover, the firmly anchored Pd nanoparticles can avoid dissolution and agglomeration during long-term use. 80.2% mass activity remained after the accelerated durability test.

Enhancing CO2 Electroreduction with Au/Pyridine/Carbon Nanotubes Hybrid Structures.

Selective electrochemical reduction of CO2 by using renewable electricity has received considerable attention because of the potential to convert a harmful greenhouse gas into useful chemicals. A high-performance electrocatalyst for CO2 reduction is constructed based on metal nanoparticles/organic molecule hybrid materials. On the nanoscale, Au nanoparticles are uniformly anchored on carbon nanotubes to afford substantially increased current density, improved selectivity for CO, and enhanced stability. On the molecular level, the catalytic performance is further enhanced by introducing axial pyridine groups to the surface of the carbon nanotubes. The resulting hybrid catalyst exhibits around 93 % faradaic efficiency for CO production over a wide potential range (-0.58 to -0.98 V), a high mass activity of 251 A gAu -1 at -0.98 V in aqueous solution at near-neutral pH, and strong stability with continuous electrolysis for 10 h at -0.58 V. DFT calculations indicate that the synergistic effects of Au and axial pyridine could dramatically stabilize the key intermediate (*COOH) formed in the rate-limiting step of CO2 reduction, which effectively lowers the overpotential.

Enzyme precipitate coating of pyranose oxidase on carbon nanotubes and their electrochemical applications.

Pyranose oxidase (POx), which doesn't have electrically non-conductive glycosylation moiety, was immobilized on carbon nanotubes (CNTs) via three different preparation methods: covalent attachment (CA), enzyme coating (EC) and enzyme precipitate coating (EPC). CA, EC and EPC of POx on CNTs were used to fabricate enzymatic electrodes for enzyme-based biosensors and biofuel cells. Improved enzyme loading of EPC resulted in 6.5 and 4.5 times higher activity per weight of CNTs than those of CA and EC, respectively. After 34 days at room temperature, EPC retained 65% of initial activity, while CA and EC maintained 9.2% and 26% of their initial activities, respectively. These results indicate that precipitation and crosslinking steps of EPC have an important role in maintaining enzyme activity. To demonstrate the feasibility of POx-based biosensors and biofuel cells, the enzyme electrodes were prepared using CA, EC, and EPC samples. In the case of biosensor, the sensitivities of the CA, EC, and EPC electrodes without BQ were measured to be 0.27, 0.76 and 3.7mA/M/cm2, while CA, EC and EPC electrode with BQ showed 25, 25, and 60mA/M/cm2 of sensitivities, respectively. The maximum power densities of biofuel cells using CA, EC and EPC electrodes without BQ were 41, 47 and 53µW/cm2, while CA, EC and EPC electrodes with BQ showed 260, 330 and 500µW/cm2, respectively. The POx immobilization and stabilization via the EPC approach can lead us to develop continuous glucose monitoring biosensors and high performing biofuel cells.