An oxygen vacancy-modulated bifunctional S-NiMoO4 electrocatalyst for efficient alkaline overall water splitting.

S-doped nickel molybdate nanorods grown on nickel foam (S-NiMoO4/NF) were fabricated by a two-step hydrothermal method. The resultant S-NiMoO4/NF exhibited remarkable bifunctional electrocatalytic activity, with overpotentials of 235 mV for the hydrogen evolution reaction and 150 mV for the oxygen evolution reaction at a current density of 50 mA cm-2. Assembled into the two-electrode S-NiMoO4/NF electrolyzer in alkaline electrolytes for overall water splitting, it required only low cell voltages of 1.55 V and 1.63 V to drive 50 mA cm-2 and 100 mA cm-2, respectively. No significant performance degradation occurred during the water electrolysis process. The experimental results confirmed that S-doping induced the increase of the oxygen vacancies, accelerating the reaction kinetics and thus improving the electrocatalytic performance. Meanwhile, more active sites exposure on the surface of S-NiMoO4/NF enhanced the reactivity. This work may guide the development of efficient bifunctional catalysts in alkaline electrolysis through oxygen vacancy regulation.

Alkali functionalized carbon nitride with internal van der Waals heterostructures: Directional charge flow to enhance photocatalytic hydrogen production.

Improving the charge separation and migration in graphitic carbon nitride (CN) is the critical issue to enhance its photocatalytic performance, but still remains very challenging. Herein, the alkali metals were introduced into the interlayer and intralayer of CN to tackle this challenge. The lithium sodium-modifying carbon nitride layer (LiNaCN2) and the adjacent CN layer formed a van der Waals heterostructures (VDWHs), while the potassium-intercalating served as interlayer charge transfer channels to induce the directional charge flow. Experiments and theoretical calculations indicated that such unique construction provided intrinsic driving force to obtain the electrons from LiNaCN2 to CN via directional potassium channels. In accordance with the theoretical prediction, a dramatically red-shift of the light absorption feature was achieved for interlayer potassium-intercalating and intralayer lithium sodium-modifying co-functionalized carbon nitride (LiNaCN-K-CN2) to show narrowed bandgap energy of 2.15 eV. This directional charge flow in CN resulted in the rapid transfer of charge carriers in both interlayer as well as intralayer of CN, which reduced the electronic localization as well as extended the π conjugative effect. Consequently, the LiNaCN-K-CN2 displayed stable and remarkable hydrogen production rate of about 2.46 mmol g-1 h-1 with apparent quantum yield (AQY) of about 13.68% at 435 nm, which was 22 folds higher than that of the pristine CN. This finding provides the feasible strategy to precisely tune the directions of charge transfer for high-performance CN-based photocatalysts.

Photoelectrocatalytic peroxymonosulfate activation over CoFe2O4-BiVO4 photoanode for environmental purification: Unveiling of multi-active sites, interfacial engineering and degradation pathways.

This work reported on the development of CoFe2O4-BiVO4 photoanode based photoelectrocatalytic system collaborating with peroxymonosulfate activation for organic contaminants removal. CoFe2O4 layer not only provided active sites for direct peroxymonosulfate activation but also accelerated charge separation process for the enhancement of photocurrent density and photoelectrocatalytic performance. Junction of CoFe2O4 layer on BiVO4 photoanode led to the improvement of photocurrent density to 4.43 mA/cm2 at 1.23 VRHE, which was approximately 4.06 times higher than that of pure BiVO4. Subsequently, the corresponding optimal degradation efficiency toward the tetracycline model contaminant achieved to be 89.1% with total organic carbon removal value of about 43.7% within 60 min. Moreover, the degradation rate constant of CoFe2O4-BiVO4 photoanode in photoelectrocatalytic system was 0.037 min-1, which was about 1.23, 2.64 and 3.70 times higher than the values in photocatalysis, electrocatalysis and PMS only based systems, respectively. In addition, radical scavenging experiments and electron spin resonance spectra indicated a synergy of radical and nonradical coupling process where •OH and 1O2 played vital roles during tetracycline degradation. Plausible photoelectrocatalytic mechanism and degradation pathway were proposed. This work provided an effective strategy to construct peroxymonosulfate assisted photoelectrocatalytic system toward green environmental applications.

N, S codoped carbon matrix-encapsulated CoFe/Co0.2Fe0.8S heterostructure as a highly efficient and durable bifunctional oxygen electrocatalyst for rechargeable zinc-air batteries.

The realization of durable and efficient oxygen evolution reactions (OER) at large current densities and low overpotentials is of significant importance but remains a great challenge. In this study, a CoFe/Co0.2Fe0.8S@NS-CNTs/CC (CF/CFS@NS-CNTs/CC) heterogeneous structure was fabricated by isolating CoFe/Co0.2Fe0.8S (CF/CFS) particles locked in nitrogen/sulfur codoped carbon nanotubes (NS-CNTs). Appreciable oxygen evolution reaction activity and durability was achieved with an ultralow overpotential of 110 mV at 10 mA•cm-2. The operation was stable for 300 h at a current density of 500 mA•cm-2. The structure was then assembled into a zinc-air battery (ZAB), which delivered a high power density of 194 mW•cm-2, a specific capacity of 837.3 mAh•gZn-1, and stable operation for 788 h without obvious voltage attenuation and altered morphology. The electronic interactions were studied by X-ray photoelectron spectroscopy (XPS), which revealed that both the bimetal components and the synergistic effect at the interface stimulated the transfer of Co and Fe sites to higher chemical valence states. Theoretical calculations indicated that the synergistic effect of the bimetal components, build-in interfacial potential, and surface chemical reconstruction adjusted the Fermi level to optimize the thermodynamic formation of O* to OOH*, thus enhancing the intrinsic activity.

Efficient Photocatalytic Hydrogen and Oxygen Evolution by Side-Group Engineered Benzodiimidazole Oligomers with Strong Built-in Electric Fields and Short-Range Crystallinity.

The insufficient charge separation and sluggish exciton transport severely limit the utilization of polymeric photocatalysts. To resolve the above issues, we incorporate bountiful carboxyl substituents within a novel benzodiimidazole oligomer and assemble it into a crystalline semiconductor. The photocatalyst is polar, hydrophilic, short-range crystalline, and capable of both hydrogen and oxygen evolution. The introduction of carboxyl side-groups adds asymmetry to the local structure and increases the built-in electric field. Further, accelerated carrier transfer is enabled via the short-range crystallinity. The superior hydrogen and oxygen production rates of 18.63 and 2.87 mmol g-1 h-1 represent one of the best performances ever reported among dual-functional polymeric photocatalysts. Our work initiates studies on high-performance oligomer photocatalysts, opening a new frontier to produce solar fuel.

Electron Donor-Acceptor Interface of TPPS/PDI Boosting Charge Transfer for Efficient Photocatalytic Hydrogen Evolution.

Charge separation efficiency of photocatalysts is still the key scientific issue for solar-to-chemical energy conversion. In this work, an electron donor-acceptor (D-A) interface with high charge separation between TPPS (tetra(4-sulfonatophenyl)porphyrin) and PDI (perylene diimide) is successfully constructed for boosting photocatalytic H2 evolution. The TPPS/PDI with D-A interface shows excellent photocatalytic H2 evolution rate of 546.54 µmol h-1 (30.36 mmol h-1 g-1 ), which is 9.95 and 9.41 times higher than that of pure TPPS and PDI, respectively. The TPPS/PDI has a markedly stronger internal electric field, which is respectively 3.76 and 3.01 times higher than that of pure PDI and TPPS. The D-A interface with giant internal electric field efficiently facilitates charge separation and urges TPPS/PDI to have a longer excited state lifetime than single component. The work provides entirely new ideas for designing materials with D-A interface to realize high photocatalytic activity.

Construction of Interfacial Electric Field via Dual-Porphyrin Heterostructure Boosting Photocatalytic Hydrogen Evolution.

A dual-porphyrin heterostructure is successfully constructed by coupling tetrakis (4-carboxyphenyl) zinc porphyrin (ZnTCPP) with tetrakis (4-hydroxyphenyl) porphyrin (THPP). The high photocatalytic H2 evolution rate of 41.4 mmol h-1 g-1 is obtained for ZnTCPP/THPP under full spectrum, which is ≈5.1 and ≈17.0 times higher than that of pure ZnTCPP and THPP, respectively. The significantly enhanced activity is mainly attributed to the giant interfacial electric field formed between dual porphyrins, which greatly facilitates efficient charge separation and transfer. Meanwhile, similar conjugated structures of dual porphyrins also provide proper interface match and decrease interface defects, thus inhibiting the recombination of photoproduced carriers. By rationally combining the appropriate band structures and high-quality interfacial contact of dual porphyrins, this work provides a fresh insight into the interfacial electric field construction to improve the photocatalytic performance.

A Full-Spectrum Porphyrin-Fullerene D-A Supramolecular Photocatalyst with Giant Built-In Electric Field for Efficient Hydrogen Production.

A full-spectrum (300-850 nm) responsive donor-acceptor (D-A) supramolecular photocatalyst tetraphenylporphinesulfonate/fullerene (TPPS/C60 ) is successfully constructed. The theoretical spectral efficiency of TPPS/C60 is as high as 70%, offering the possibility of full-solar-spectrum light harvesting. The TPPS/C60 performs a highly efficient photocatalytic H2 evolution rate of 276.55 µmol h-1 (34.57 mmol g-1 h-1 ), surpassing many reported organic photocatalysts. The D-A structure effectively promotes electron transfer from TPPS to C60 , which is beneficial to the photocatalytic reaction. Specifically, a giant internal electric field in the D-A structure is built via the enhanced molecular dipole, which dramatically promotes the charge separation (CS) efficiency by 2.35 times. Transient absorption spectra results show a long-lived CS state TPPS•+ -C60 •- in the D-A structure, which effectively promotes participation of photogenerated electrons in the reduction reaction. Briefly, this work provides a novel approach for designing high-performance photocatalytic materials via enhancing the interfacial electric field.

The Acidities of Nucleophilic Monofluoromethylation Reagents: An Anomalous α-Fluorine Effect.

Fluorine incorporation into organic molecules is expected to lower the pKa of neighboring functionality via its strong electron-withdrawing effect, and this strategy has been widely exploited in diverse disciplines. Herein, we report a striking anomalous α-fluorine substitution effect on the α-Csp3 -H acidity. We have experimentally measured the pKa values of a series of popular nucleophilic monofluoromethylating reagents α-fluoro(phenylsulfonyl)methane derivatives as well as their C-H analogues by Bordwell's overlapping indicator method in dimethyl sulfoxide solution. Contrary to expectations, we found that α-fluorine substituent does not generally enhance but rather weaken the α-Csp3 -H acidity of most (phenylsulfonyl)methane derivatives. DFT computations reproduce and provide insight into the anomalous α-fluorine effect. A correlation was identified between the C-H pKa of (phenylsulfonyl)methane derivatives and Mayr's nucleophilicity parameter (N) of the corresponding carbanions.