Accurate design of spatially separated double active site in Bi_(4)NbO_(8)Cl single crystal to promote Z-Scheme photocatalytic overall water splitting

The efficiency of photocatalytic overall water splitting was mainly limited by the slow reaction kinetics of water oxidation.How to design effective surface active site to overcome the slow water oxidation reaction was a major challenge.Here,we propose a strategy to accelerate surface water oxidation through the fabrication spatially separated double active sites.FeCoPi/Bi_(4)NbO_(8)Cl-OVs photocatalyst with spatially separated double active site was prepared by hydrogen reduction photoanode deposition method.Due to the high matching of the spatial loading positions of FeCoPi and OVs with the photogenerated charge distribution of Bi_(4)NbO_(8)Cl and corresponding reaction mechanisms of substrate,the FeCoPi and OVs on the(001)and(010)crystal planes of Bi_(4)NbO_(8)Cl photocatalyst provided surface active site for water oxidation reaction and electron shuttle reaction(Fe^(3+)/Fe^(2+)),respectively.Under visible light irradiation,the evolution O_(2)rate of FeCoPi/Bi_(4)NbO_(8)Cl OVs was 16.8μmol h^(-1),as 32.9 times as Bi_(4)NbO_(8)Cl.Furthermore,a hydrogen evolution co-catalyst PtRu@Cr_(2)O_(3)was prepared by sequential photodeposition method.Due to the introduction of Ru,the Schottky barrier between PbTiO_(3)and Pt was effectively reduced,which promoted the transfer of photogenerated electrons to PtRu@Cr_(2)O_(3)thermodynamically,the evolution H_(2)rate on PtRu@Cr_(2)O_(3)/PbTiO_(3)increased to 664.8 times.On based of the synchronous enhancement of the water oxidation performance on FeCoPi/Bi_(4)NbO_(8)Cl-OVs and water reduction performance on PtRu@Cr_(2)O_(3)/PbTiO_(3),a novel Z-Scheme photocatalytic overall water splitting system(FeCoPi/Bi_(4)NbO_(8)Cl-OVs)mediated by Fe^(3+)/Fe^(2+)had successfully constructed.Under visible light irradiation,the evolution rates of H_(2)and O_(2)were 2.5 and 1.3μmol h^(-1),respectively.This work can provide some reference for the design of active site and the controllable synthesis of OVs spatial position.On the other hand,the hydrogen evolution co catalyst(PtRu@Cr_(2)O_(3))and the co catalyst FeCoPi for oxygen evolution contributed to the construction of an overall water splitting system.

Double active sites promoting hydrogen evolution activity and stability of CoRuOH/Co_(2)P by rapid hydrolysis

Cobalt-based phosphides show excellent hydrogen evolution reaction(HER)performance,however,improving the intrinsic activity and stability of it in alkaline electrolyte still remains a challenge.Herein,CoRuOH/Co_(2)P/CF with heterojunction structure was developed by means of molten salt and rapid hydrolysis(30 s).The OH-from rapid surface hydrolysis of Co_(2)P as a hydrogen adsorption site can facilitate the formation of thin CoRuOH layer as a water dissociation site,which may bring out better synergistic effect for alkaline HER.Moreover,the covering of CoRuOH can improve the stability of Co_(2)P for HER.When drives at 100 mA/cm^(2),it only requires overpotential of 81 mV in 1.0 mol/L KOH(25℃).Even at higher current density(1000 mA/cm^(2)),CoRuOH/Co_(2)P/CF can also operate stability for at least 100 h.When coupling with NiFe-LDH/IF in a two-electrode system,the voltage of NiFe-LDH/IF(+)||CoRuOH/Co_(2)P/CF(-)at 1000 mA/cm^(2)is merely 1.77 V with 100 h,demonstrating great potential for water splitting.The implementation of this work provides a new strategy and reference for the further improvement of transition metal phosphides as HER electrocatalysts.

Controlled high-density interface engineering of Fe_(3)O_(4)-FeS nanoarray for efficient hydrogen evolution

The rational design of double active sites system is vital for constructing high-efficiency iron sulfides electrocatalysts towards hydrogen evolution reaction(HER) in alkaline media. However, it remains a challenge to controllably create the high-density interface of double sites for optimal synergistic effect.Herein, we reported a simple chemical oxidation-induced surface reconfiguration strategy to obtain the interface-rich Fe_(3)O_(4)-FeS nanoarray supported on iron foam(Fe_(3)O_(4)-FeS/IF) using FeS nanosheets as precursors. The abundant Fe_(3)O_(4)-FeS interfaces could improve the dispersion of active sites and facilitate the electron transfer, leading to enhanced hydrogen evolution efficiency. And meanwhile, by altering the oxidation temperature, the content of S and O could be effectively controlled, further achieving the ratio optimization of Fe_(3)O_(4)to FeS. Synchrotron-based X-ray absorption near-edge structure, X-ray photoelectron spectroscopy and ultraviolet photoemission spectroscopy consistently confirm the changes of electronic structure and d-band center of Fe_(3)O_(4)-FeS after chemical oxidation. Consequently, Fe_(3)O_(4)-FeS/IF exhibits excellent alkaline HER activity with a low overpotential of 120.8 mV to reach 20 mA cm^(-2),and remains stable ranging from 10, 20 to 50 mA cm^(-2) for each 20 h, respectively. Therefore, the facile and controllable chemical oxidation may be an effective strategy for designing high-density interfaces of transition metal-based sulfides towards alkaline HER.

Self-templated nitrogen-doped mesoporous carbon decorated with double transition-metal active sites for enhanced oxygen electrode catalysis

The development of high-performance,low-cost bifunctional catalysts with long-term stability for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is one of the most critical challenges for the large-scale application of metal-air batteries.Herein,we report an advanced nitrogen-doped mesoporous carbon(NMC)composite(NiCo2O4/CoNx-NMC)formed from a mixture of Co-and Ni-hydroxide-infiltrated phenolic resin and melamine resin.This composite exhibits superior electrocatalytic activity,stability,and selectivity for the ORR and OER.The activity parameter(DE),which is an indicator of the overall catalytic activity of bifunctional catalysts,was 0.76 V for NiCo2O4/CoNx-NMC.Therefore,catalyst outperforms the majority of previously reported non-precious metal-based bifunctional electrocatalysts.The remarkable ultra-high catalytic performance of NiCo2O4/CoNx-NMC for the ORR and OER can be attributed to the presence of different active sites of the CoNx structure and the formation of NiCo2O4 with the spinel structure,which was obtained by a stepwise pyrolysis process.This synthesis strategy opens a new avenue for the rational design of highly active bifunctional electrocatalysts.

Bidirectional catalysis of Co_(0.4)Ni_(1.6)P for Li_(2)S_(1-2) deposition/decomposition reactions in Li-S batteries

To improve the electrochemical activity of S electrodes in Li-S batteries,the synergistic electrocatalysis mechanism of Co_(0.4)Ni_(1.6)P with Ni and Co bimetal interactions is clarified.The alternating crystal structure of Co and Ni regulates the adsorption and decomposition energy of Co_(0.4)Ni_(1.6)P to polysulfides and has the bidirectional catalysis for the Li_(2)S_(1-2)deposition/decomposition process.Co_(0.4)Ni_(1.6)P can promote the breaking of the S-S bond of Li_(2)S_(4) and decrease the decomposition energy barrier of Li_(2)S.This regulation accelerates the discharge/charge reaction between S,polysulfides,and Li_(2)S and improves the kinetics of the S electrodes.The 1st,100^(th),and 200^(th) discharge capacity densities at 0.1 mA cm^(-2) of the S electrodes with a high sulfur loading were 1,405,987.2,and 828.4 m Ah gS^(-1),respectively.The bidirectional catalytic mechanism is a novel idea for improving the electrochemical performance of Li-S batteries.

Repaired morphology of CO_(2)laser rapid ablation mitigation of fused silica and its influence on downstream light modulation

The threat of cascading damage to downstream components caused by the light modulation intensification of laser repaired morphology on the surface of fused silica optics cannot be ignored in high-power laser systems.This paper uses the angular spectrum diffraction theory based on the analysis of repaired surface morphology of CO_(2)laser rapid ablation mitigation to study the influence of different repaired morphologies on the downstream 355 nm laser transmission.Studies show that the arc-shaped laser processing lines on the repaired surface are formed by the residual height superposition of the material after laser scanning of two adjacent layers,and the short-pulse laser can substantially suppress the heat-affected zone of the repaired area.The offaxis ring caustic and on-axis hotspot are sequentially generated in the downstream modulated light fields of the conical repaired sites with different diameters.A secondary peak with modulation larger than 3 emerges downstream of the modulation curve.Meanwhile,the maximum modulation and the secondary peak increase with the diameter and cone angle of the repaired site,and the position of the secondary peak appears farther away from the rear surface.The modulations of three repaired sites with cone angles of 15°,20°,and 25°can finally be stabilized below 3.Overall,the downstream optics should be installed far away from the positions where the maximum modulation and the secondary peak emerge.Additionally,the maximum value and the secondary peak of the downstream light modulation of double repaired sites are larger than that of the single repaired site,and both rise as the repaired sizes increase.Thus,large-scale and large-size repairing of multiple surface damages in the same area should be avoided in the laser repairing of fused silica.