Modification Of Active Site Research Articles

Confinement of Z-scheme organic-inorganic heterojunction into mesoporous zeolite for efficient photocatalytic solar fuel generation

Organic-inorganic heterojunction has drawn increasing interest in photocatalytic CO2 reduction (PCR) by immobilizing molecular catalysts on inorganic semiconductors. However, it is difficult to control the size and dispersion of inorganic semiconductors during the assembling process, which restricts the PCR performance due to limited active sites and charge separation efficiency. Herein, we utilized a commercial mesoporous zeolite (SBA-15) to confine TiO2 via an in situ approach followed by assembling with a Co(II) tetra(4-carboxylphenyl) porphyrin (Co-TCPP). As a result, a Z-scheme organic–inorganic heterojunction of TiO2/SBA-15@Co-TCPP was obtained, which demonstrated superior PCR performance among simulated solar light irradiation. The optimized TiO2/SBA-15@Co-TCPP demonstrated improved solar fuel evolution (241.63 μmolco g−1) via PCR process when compared to bulk TiO2 or pristine Co-TCPP. The experiment results and density functional theory (DFT) calculations reveal the superior PCR performance induced by the extended light-harvesting region from the Z-scheme heterojunction, elevated PCR selectivity induced by the hydrophilicity of SBA-15 and molecular Co(II) center, enhanced charge separation owing to the highly dispersed nanosized TiO2 and inner-building electronic field. This work highlights the importance of mesoporous zeolite substrate in control of the PCR activity and selectivity, which hold great potential to develop multiple zeolite-based heterojunctions for efficient solar-driven fuel generation.

Enhanced NO2 Gas Sensing in Nanocrystalline MoS2 via Swift Heavy Ion Irradiation: An Experimental and DFT Study.

Nanostructured transition metal dichalcogenides (TMDs) like MoS2 hold promise for gas sensing applications due to their exceptional properties. However, limitations exist in maximizing sensor performance, such as limited active sites for gas interaction and sluggish response/recovery times. This study explores swift heavy ion (SHI) irradiation as a strategy to address these challenges in MoS2-based NO2 gas sensors. MoS2 nanoflakes were fabricated and subsequently irradiated with 120 MeV silver (Ag) ions to induce structural and morphological modifications. Characterization techniques confirmed the formation of Mo and S vacancies within the MoS2 lattice due to irradiation. Significantly, SHI irradiation resulted in a remarkable enhancement of approximately 3 times improvement in sensing response compared to pristine MoS2 sensors. Additionally, the irradiated sensors exhibit substantial improvements in both response and recovery times for NO2 detection. SHI irradiation resulted in the formation of self-affine nanostructures and increased grain fragmentation as fluence rises. This enhanced surface area is hypothesized to promote gas-sensor response. To gain deeper insights into the underlying mechanism, first-principles calculations were employed. These calculations suggest that electron transfer occurs from the MoS2 surface to the NO2 molecule during interaction. Furthermore, the irradiation-induced vacancies facilitate stronger NO2 adsorption on the MoS2 surface compared to the pristine sample. This work demonstrates the effectiveness of SHI irradiation in engineering defects within MoS2 nanoflakes, leading to significantly improved NO2 gas-sensing performance. This approach offers a promising avenue for developing next-generation TMD-based gas sensors with enhanced sensitivity, response times, and stability.

A recyclable and high porosity vinasse-based biochar with enhanced superficial active sites for antibiotics recovery

Antibiotic pollution in water bodies is a global environmental issue. For adsorbing antibiotic residues, biochar produced by direct high temperature pyrolysis faces challenges in balancing adsorption capacity and recyclability due to limited active sites. Thus, a recyclable and high-porosity vinasse-based biochar was developed via co-pyrolysis of K2FeO4 one-pot method. The co-pyrolysis biochar's surface area was augmented by 143 times, from 3.4 m²/g to 490.9 m²/g. The maximum theoretical adsorption capacity of the co-pyrolysis biochar for norfloxacin (NOR) increased from 4.4 mg/g to 364.9 mg/g, an approximate 83-fold enhancement. The surface of the biochar was rich in active groups (C-O, C-Fe, and -OH), which acted as the active sites to enhance the adsorption of NOR. The adsorption mechanism involved a variety of interactions, including pore-filling, hydrogen bond, π-π interactions, surface complexation, and electrostatic interactions. Importantly, the biochar is magnetic and can be recycled attributed to the generation of ferriferous oxides during the carbonization. After three cycles of reuse, the adsorption efficiency of vinasse-based biochar for NOR still exceeded 70 %. Such biochar prepared by this facile and feasible co-pyrolysis method show the potential to enhance active sites for removal of antibiotic from aquatic systems.

In-Situ Construction of Atomic-Level Fe-O Bond Bridges within Fe2N/g-C3N4 Heterojunction for Efficient Visible-Light-Driven Photocatalytic H2 Production.

The limited active sites and faster photogenerated electron-hole pair recombination rate of g-C3N4 restrict its application in photocatalytic H2 production. Constructing heterojunctions has been shown to improve the spatial (directional) separation of photogenerated electrons and holes. However, due to interface mismatch in traditional heterojunction structures and a lack of precise electron transport channels, the photocatalytic efficiency is limited. Here, we developed a two-step calcination approach to create an Fe2N/g-C3N4 heterojunction linked by Fe-O bonds (named as Fe-OCN). The newly formed Fe-O bonds within the heterojunction can act as atomic-level interface electron transfer channels, directly transferring the photogenerated electrons of g-C3N4 to the reactive center Fe2N, significantly improving the charge transfer rate and utilization, thus promoting visible-light-driven photocatalytic H2 production. The optimal Fe-OCN achieved a H2 production rate of 5986.29 μmol g-1 h-1 under visible light, 13.44 times higher than that of the OCN due to efficient charge separation and transfer capabilities. This work provides a constructive reference for the design and synthesis of organic-inorganic heterojunction with chemically bonded interfaces, establishing quick electron transfer channels, and achieving targeted electron transfer.

Regulating V2O5 Layer Spacing by a Polyaniline Molecule Chain to Improve Electrochemical Performance in Salinity Gradient Energy Conversion.

Salinity gradient energy is a chemical potential energy between two solutions with different ionic concentrations, which is also an ocean energy at the junction of rivers and seas. In our original work, the device "activated carbon//(0.083 M Na2SO4, 0.5 M Na2SO4)//vanadium pentoxide" for the conversion of salinity gradient energy was designed, and the conversion value of 6.29 J g-1 was obtained. However, the low specific surface area of the original V2O5 inevitably resulted in limited active sites and slow ionic transport rates, and the inherent lower conductivity and narrower layer spacing of the original V2O5 also resulted in poor electrode kinetic performance and cycle stability, hindering its practical application. To solve the above problems, the present work provides a strategy of using polyaniline (PANI) molecule chain intercalation to regulate the layer spacing of the original V2O5, and through the expansion and traction of the layer spacing, the composite PANI/V2O5 (PVO) with high specific surface area is prepared and used as an anode material for electrochemical conversion of salinity gradient energy application. The significantly increased layer spacing of the crystal plane (001) corresponding to the original V2O5 was confirmed with the PANI by the hydrogen bonding and the van der Waals force. The high specific surface area of the composite provides more electrochemical active sites to realize a fast Na+ migration rate and high specific capacitance. Meanwhile, the inserted PANI molecule chain, which acts not only as a pillar enlarging the Na+ diffusion channel but also as an anchor locking the gap between V2O5 bilayers, improves the structural stability of the V2O5 electrode during the electrochemical conversion process. The proposed insertion strategy for the conductive polymer PANI has created a new way to improve the cycle stability performance of the salinity gradient energy conversion device.

Advances in hybrid strategies for enhanced photocatalytic water splitting: Bridging conventional and emerging methods

Significant efforts have been dedicated to hydrogen production through photocatalytic water splitting (PWS) over the past five decades. However, achieving commercially viable solar-to-hydrogen conversion efficiency in PWS systems remains elusive. These systems face intrinsic and extrinsic challenges, such as inadequate light absorption, insufficient charge separation, limited redox active sites, low surface area, and scalability issues in practical designs. To address these issues, conventional strategies including heterojunction engineering, plasmonics, hybridization, lattice defects, sensitization, and upconversion processes have been extensively employed. More recently, innovative hybrid strategies like photonic crystal-assisted and polarization field-assisted PWS have emerged, which improve light absorption and charge separation by harnessing the slow photon effect, multiple light scattering, and the piezoelectric, pyroelectric, and ferroelectric properties of materials. This review article aims to provide a comprehensive examination and summary of these new synergistic hybrid approaches, integrating plasmonic effects, upconversion processes, and photonic crystal photocatalysis. It also explores the role of temperature in suppressing exciton recombination during photothermic photocatalysis. This article also highlights emerging strategies such as the effects of magnetic fields, periodic illumination, many-body large-hole polaron, and anapole excitations, which hold significant potential to advance PWS technology and facilitate renewable hydrogen generation.

Metal-organic framework-derived silver/copper-oxide catalyst for boosting the productivity of carbon dioxide electrocatalysis to ethylene

Electrochemical reduction of CO2 into valuable multi-carbon (C2) chemicals holds promise for mitigating CO2 emissions and enabling artificial carbon cycling. However, achieving high selectivity remains challenging due to the limited activity and active sites of CC coupling catalysts. Herein, we report an Ag-modified Cu-oxide catalyst (CuO/Ag@C) derived from metal-organic frameworks (MOF), capable of efficiently converting CO2 to C2H4. The MOF-derived porous carbon confines the size of metal nanoparticles, ensuring sufficient exposure of active sites. Remarkably, the CuO/Ag@C catalyst achieves an impressive Faradaic efficiency of 48.6% for C2H4 at −0.7 V vs. RHE, demonstrating excellent stability. Both experimental results and theoretical calculations indicate that Ag sites promote the production of CO, enhancing the coverage of *CO on Cu sites. Furthermore, the reconfiguration of charge density at the Cu-Ag interface optimizes the electronic states of the reaction sites, reducing the formation energy of the key intermediate *OCCHO, thereby favoring C2H4 production effectively. This work provides insight into structurally rational catalyst design for highly active and selective multiphase catalysts.

Advancements in Rechargeable Zn-Air Batteries with Transition-Metal Dichalcogenides as Bifunctional Electrocatalyst.

This review covers recent progress on transition metal dichalcogenides (TMDs) as bifunctional electrocatalysts for Zinc-air batteries (ZABs), emphasizing their suitable surface area, electrocatalytic active sites, stability in acidic/basic environments, and tunable electronic properties. It discusses strategies like defect engineering, doping, interface, and structural modifications of TMDs nanostructures for enhancing the performances of ZABs. Zinc-air batteries are promising energy storage devices owing to their high energy density, low cost, and environmental friendliness. However, the development of durable and efficient bifunctional electrocatalysts is a major concern for Zn-air batteries. In this review, we summarize the recent progress on transition metal dichalcogenides (TMDs) as bifunctional electrocatalysts for Zn-air batteries. We discuss the advantages of TMDs, such as high activity, good stability, and tunable electronic structure, as well as the challenges, such as low conductivity, poor durability, and limited active sites. We also highlight the strategies for fine-tuning the properties of TMDs, such as defect engineering, doping, hybridization, and structural engineering, to enhance their catalytic performance and stability. We provide a comprehensive and in-depth analysis of the applications of TMDs in Zn-air batteries, demonstrating their potential as low-cost, abundant, and environmentally friendly alternatives to noble metal catalysts. We also suggest future directions like exploring new TMDs materials and compositions, developing novel synthesis and modification techniques, investigating the interfacial interactions and charge transfer processes, and integrating TMDs with other functional materials. This review aims to illuminate the path forward for the development of efficient and durable Zn-air batteries, aligning with the broader objectives of sustainable energy solutions.

Carboxymethylcellulose Induced the Formation of Amorphous MnO2 Nanosheets With Abundant Oxygen Vacancies for Fast Ion Diffusion in Aqueous Zinc‐Ion Batteries

AbstractManganese dioxide with high theoretical capacity has drawn a great deal of attention for aqueous zinc‐ion batteries (ZIBs). Nevertheless, their sluggish diffusion kinetics, low electrical conductivity and limited active sites are still hindering the potential application in batteries. Herein, amorphous MnO2 nanosheets with abundant oxygen vacancies are facilely prepared by using carboxymethylcellulose sodium (CMC) as a capping agent. During the growth process, CMC can preferentially attach to the (003) facet of MnO2 to guide its crystal growth and morphology. The small nanosheets can expose abundant edge sites, along with the surface oxygen vacancies, to facilitate the insertion/extraction of H+ and Zn2+ in ZIBs. Moreover, the presence of CMC can stabilize the Mn3+ to inhibit the Jahn–Teller effect in the preparation process. As a result, CMC‐MnO2 based ZIB can provide a specific capacity of 324 mAh g−1 at 0.5 A g−1, and achieve 86.2% retention after a long cycle test of 1000 cycles. Furthermore, the energy storage mechanism may be attributed to the insertion/extraction of H+/Zn2+, dissolution/deposition of MnO2 and Zn4SO4(OH)6·nH2O, and irreversible transformation of vermiculite during long cycles. This work may open new perspectives for the development of MnO2‐based cathodes in ZIBs.

Sulfur-vacancy induced asymmetric active site for Bi19S27Br3 nanorods photocatalyzes CO2 conversion to ethylene

The photocatalytic conversion of CO2 into high value-added C2 products remains a significant challenge due to the limited active sites and high energy barrier of C-C coupling process. Herein, the sulfur-vacancy was established on the surface of Bi19S27Br3 nanorods, leading to the electron on residual S atoms become unstable and active. Under the light irradiation, the photoexcited electron transfer from S atoms to neighboring Bi atoms to generate in-situ charge-polarized Bi(3-x)+ asymmetric active sites, which can enhance CO2 adsorption-activation capacity and regulate C-C coupling process for the C1 intermediate. The experimental results and theoretical calculation confirm that more charges aggregate around the induced Bi atoms, reducing the energy barrier of the C-C coupling reaction and improving C2H4 formation. Consequently, the sulfur-vacancy Bi19S27Br3 nanorods achieve efficient C2H4 generation through photocatalytic CO2 reduction, which C2H4 formation rate is 17.80 µmol g−1 after 5-hour photocatalytic reaction, with the product selectivity and electron selectivity of 49 % and 85 %, respectively, outperforming the low sulfur-vacancy Bi19S27Br3 nanorods by four-folds. This research provides new insights into the design of photocatalysts.

Integrated electrochemical-adsorption for simultaneous removal of pharmaceuticals from water: Process optimization and synergistic insights

Water contamination with pharmaceuticals has become an evident environmental challenge. Treatment processes such as electrochemical oxidation (EO) and adsorption have limitations in the simultaneous removal of pharmaceuticals from water. Therefore, this study examined the potential of coupled process (EO followed by adsorption) in binary pharmaceuticals (acetaminophen (ACM) + ciprofloxacin (CIP)) removal from water, with an emphasis on coupled process optimization. Consequently, optimized coupled process conditions including current density (22 mA/cm2), pH (5.5), EO time (40 min), adsorbent dose (0.1 g/L) and adsorption time (60 min) were obtained. Under optimal conditions, removal efficiencies of 94.6% (ACM)+92% (CIP), 94.07% (ACM)+91.15% (CIP), and > 99.8% (ACM + CIP) were recorded for 20 mg/L (ACM + CIP) removal in EO, adsorption and EO + adsorption, respectively. Further, the coupled process was employed in multiple pharmaceuticals (20 mg/L of ACM + CIP + ATN (atenolol) + AMX (amoxicillin)) removal from water and removal of > 97.56% (ACM + CIP + ATN + AMX) was achieved. Removal efficiencies of ACM (83.35%) + CIP (73.1%) + ATN (68.52%) + AMX (63.05%) and ACM (80.37%) + CIP (66.5%) + ATN (73.07%) + AMX (60.5%) were obtained in EO and adsorption, respectively. The noted lower removal efficiencies in EO and adsorption are associated with the diverse nature of the pharmaceuticals, limited adsorbent active sites, and the shared utilization of reactive oxygen species (ROS) among the pharmaceuticals in EO. The total organic carbon (TOC) removal of 40.24%, and 99% and chemical oxygen demand (COD) removal of 72.45%, and 99.6% were obtained under optimal conditions of EO, and coupled process, respectively. These findings indicate that the pharmaceuticals are only partially mineralized in EO and the subsequent adsorption effectively eliminated the remaining target pharmaceuticals, and degradation by-products from water. Additionally, integrating EO with adsorption reduced the electrical energy consumption of the EO process from 31.6 kWh/m³ to 6 kWh/m³ under optimal conditions. Overall, coupling EO with adsorption offers the utmost advantages when removing multiple pharmaceuticals from complex water matrices.

Chronic environmental level exposure to perfluorooctane sulfonate overshadows graphene oxide to induce apoptosis through activation of the ROS-p53-caspase pathway in marine medaka Oryzias melastigma

The widespread occurrence of perfluorooctane sulfonate (PFOS) and the mass production and application of graphene oxide (GO) lead to their inevitable release and interaction in the environment, which may enhance associated toxic impacts on aquatic organisms. This study elucidates the induction of apoptosis by 60-day chronic single and mixture exposures to environmentally relevant levels of PFOS (0.5 μg/L and 5 μg/L) and GO (1 mg/L) in adult marine medaka Oryzias melastigma. Results showed a significant increase (p < 0.05) in reactive oxygen species (ROS) levels, the apoptotic positive rate in livers, and activities of caspases 3, 8, and 9 in all treated groups compared to the control. PFOS individual and PFOS-GO combined exposures significantly impacted fish growth, upregulated expressions of six apoptosis-related genes including p53, apaf1, il1b, tnfa, bcl2l1, bax, as well as enriched cell cycle and p53 signaling pathways (transcriptomic analysis) related to apoptosis compared to control group. Besides higher ROS production, GO also had a higher binding affinity to proteins than PFOS, especially to caspase 8 as revealed by molecular docking. Overall, PFOS induced ROS-p53-caspase apoptosis pathway through multi-gene regulation during single or mixture exposure, while GO single exposure induced apoptosis through tissue damage and ROS-caspase pathway activation and direct docking with caspase 8 to activate the caspase cascade. Under co-exposure, the PFOS-induced apoptotic pathway overshadowed the GO-induced pathway, due to competition for limited active sites on caspases. These findings will contribute to a better understanding of the apoptosis mechanism and ecological risks of nanomaterials and per- and polyfluoroalkyl substances in marine ecosystems.

Dual polarization in CoMoO4-NiMoO4 heterojunction boosted electrochemical charge storage

Binary transition metal oxides (BTMOs) stand out as a focal point due to their distinctive electrochemical properties. However, they encounter challenges like low conductivity and limited active sites. To tackle these obstacles, we have meticulously designed a CoMoO4-NiMoO4 (CMNM) heterostructure featuring significant compressive-tensile strain. This design facilitates the robust integration of CoMoO4 (CM) and NiMoO4 (NM), initiating interfacial polarization, and establishing a built-in electric field (BIEF) that significantly enhances electron transfer between the phases. Moreover, the strain serves as a driving force for the electric field, promoting the rearrangement of interface electrons and further boosting interfacial polarization. This avant-garde approach propels the CMNM electrode to achieve a remarkable specific capacity of 530.45 C g−1 at 1 A g−1, maintaining 327 C g−1 even at 10 A g−1, thus showcasing a superior rate capability. Furthermore, an asymmetric supercapacitor employing CMNM as the positive and FeOOH as the negative achieves a high energy density of 78.9 Wh kg−1 at a power density of 927.02 W kg−1. Our methodology, leveraging heterostructures coupled with the interfacial strain tactics, paves a novel avenue for high-performance supercapacitors.

Rational Construction of Heterostructures with n‐Type Anti‐Barrier Layer for Enhanced Electrochemical Energy Storage

AbstractAs a type of 2D materials, layered double hydroxides (LDHs) have emerged as potential candidates for electrochemical energy storage materials. To address their challenges of limited active sites and sluggish charge transfer kinetics, etc., this work presents an ingenious synchronous topochemical pathway (STP) method that enables the in situ anchoring of numerous nanosized Co9S8 on the rigid layers of LDHs. These n‐type anti‐barrier layers, generated by the ohmic contact between a quasi‐metal (Co9S8) and n‐type semiconductor (LDHs), alter the energy band structure and electron states near the Fermi level, optimizing the intrinsic conductivity and deprotonation reaction barriers of LDH materials. The prepared NiCoAl‐LDHs@Co9S8 (LCS) electrode exhibits remarkable electrochemical capacity (473.2 mAh g−¹ at 1 A g−¹) and operational stability (91.2% capacity retention after 20,000 cycles). Furthermore, an aqueous battery device constructed with LCS cathode and Fe‐Ni sulfide (FNS) anode demonstrates an impressive energy density of 118.5 Wh kg−¹ at a power density of 800 W kg−¹. This generalized structural design strategy achieves multiple enhancements in active sites, charge transfer efficiency, and structural stability of LDH materials, providing insights into the potential relationships between energy band and electrochemical performance in energy storage materials.

Vacancy-rich heterogeneous MnCo2O4.5@NiS electrocatalyst for highly efficient overall water splitting

Alkaline water electrolysis is regarded as a promising technology for sustainable energy conversion. Spinel oxides have attracted considerable attention as potential catalysts because of their diverse metal valence states. However, achieving the required current densities at low voltages is a challenge due to its limited active sites and suboptimal electron transport. In this study, we present a novel bifunctional catalyst composed of MnCo2O4.5 nanoneedles grown on NiS nanosheets for water electrolysis. Remarkably, MnCo2O4.5@NiS demonstrates exceptional catalytic activity, requiring 187 and 288 mV to achieve a current density of 100 mA cm−2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. The impressive performance of MnCo2O4.5@NiS is demonstrated by the lower value of voltage 1.44 V needed to deliver the current density of 10 mA cm−2, which outperformed the 1.66 V required for a commercial Pt/C||RuO2 system. Detailed structure analysis and density functional theory (DFT) calculations reveal that the MnCo2O4.5@NiS heterostructure enhances electron transfer at the interface, promotes the formation of oxygen vacancies and tunes the electronic structures of Mn and Co. These findings underscore the potential of MnCo2O4.5@NiS as an efficient and cost-effective electrocatalyst for hydrogen production.

Hollow-structured and nano-flower shaped high entropy layer double hydroxide for superiority specific capacitance and rate capability of supercapacitor

High entropy hydroxide as electrode materials has been widely studied in the field of supercapacitors, but due to the limited active site and poor conductivity, it usually shows poor specific capacity and magnification performance, which seriously limit its development in the field of supercapacitors. In this work, a hollow-structured and nano-flower shaped high entropy layer double hydroxide was synthesized by the double template method combined with nano-etching to achieve superiority specific capacitance and rate capability of supercapacitor. The experimental and theoretical results indicate that the specific capacitance of this novel electrode material is as high as 1820.1 F·g−1. In particular, after the current density was increased by 40 times, the specific capacitance can reach 1140.2 F·g−1, and its electrochemical performance is higher than most of high entropy electrode materials reported so far. More importantly, the S-HE-LDH//AC HSC was constructed with the material as the electrode. It has an energy density of 74.2 Wh·kg−1 at 475 W·kg−1 power density. After 5000 cycles, the specific capacitance of the HSC device can still maintain 90.8 % of its initial value. These results indicate that the electrochemical properties of LDHs can be effectively improved by the combination of microstructure adjustment and electronic structure optimization.

Revealing the role of 1T- & 2H- molybdenum Disulfide/Nickel sulfide heterojunction for efficient overall water splitting

In the ongoing quest for cost-effective and durable electrocatalysts for hydrogen production—a critical element of sustainable energy transformation—the 1T phase of Molybdenum Disulfide (MoS2) faces challenges due to its thermodynamic instability and the trade-off between efficiency and durability. Conversely, the 2H phase of MoS2, often disregarded in favor of the metallic 1T phase, suffers from its inert nature and limited active sites. To overcome these limitations, this study employs a straightforward hydrothermal synthesis strategy that couples both 1T and 2H phases of MoS2 with Ni3S2, forming 1T- and 2H- MoS2/Ni3S2 heterojunctions. Enhanced by Ni3S2′s abundant active sites, improved electron transport capabilities, synergistic interface effects, and better structural stability, these heterojunctions achieve a high current density exceeding 500 mA cm−2 at low overpotentials, along with prolonged durability for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline electrolytes. Remarkably, an electrolyzer assembly utilizing 1T-MoS2/Ni3S2 as the cathode and 2H-MoS2/Ni3S2 as the anode demonstrates a competitive voltage of 1.58 V at 20 mA cm−2, showcasing superior performance in overall water splitting compared to other non-noble metal-based electrocatalysts. This study not only offers a viable method for synthesizing efficient and stable electrocatalysts for water splitting using transition metal-based heterogeneous structures but also addresses the fundamental challenges associated with 1T and 2H phases of MoS2.

Interface Engineering of VOx/Ni/Ni3N Heterostructures for Electrochemical Urea-Assisted Hydrogen Production.

Electrocatalytic hydrogen generation driven by renewable energy sources is severely limited by the slow oxygen evolution reaction (OER). Urea-assisted alkaline hydrogen production offers a perspective approach. However, the construction of efficient and robust anode catalysts is still challenging. Herein, an amorphous/crystalline VOx/Ni/Ni3N-heterostructured catalyst grown on carbon cloth was synthesized and used as a bifunctional electrocatalyst for the hydrogen evolution reaction (HER) and urea electrooxidation reaction (UOR). Benefiting from the electronic modification of intercomponents and abundant active sites, VOx/Ni/Ni3N exhibits an excellent electrochemical performance toward the HER and UOR. Theoretical calculations confirmed that the crystalline/amorphous VOx/Ni/Ni3N heterostructure has a suitable water dissociation energy and H* adsorption energy, thereby promoting the HER process. When the UOR and HER are integrated into an electrolytic device, VOx/Ni/Ni3N requires a potential of 1.40 V to achieve a current density of 10 mA cm-2.

Dipole polarization-driven spatial charge separation in defective zinc cadmium sulfoselenide for boosting photocatalytic hydrogen evolution

The industrial interest of ZnCdS as the photocatalytic media for hydrogen evolution reaction (HER) is severely hindered by its sluggish interfacial charge transfer, limited active sites, and serious photocorrosions. Herein, to catalyze more efficient and robust HER, a series of Se-doped ZnCdS with sulfur vacancies (denoted as Se/VS-ZnCdS) are ingeniously designed and facilely synthesized. Experimental and theoretical studies reveal that by inducing dipole polarization through defect engineering synergistic elemental doping, spontaneous polarization field is generated in the bulk phase of ZnCdS, which together with elevated Fermi level renders the Se/VS-ZnCdS with desirable spatial charge separation and transfer. Thus, the optimal 0.6 %Se/VS-ZnCdS exhibits the outstanding performance of 85.3 mmol·gcat−1·h−1 and excellent stability up to 24 h. This work highlights the high efficiency of dipole polarization realized by vacancy synergistic atomic doping in optimizing HER kinetics, and provides a new pathway to develop robust photocatalysts based on metal sulfoselenide for water-splitting reactions.

Biocatalytic Synthesis of Ruxolitinib Intermediate via Engineered Imine Reductase.

An enzyme catalyzed strategy for the synthesis of a chiral hydrazine from 3-cyclopentyl-3-oxopropanenitrile 5 and hydrazine hydrate 2 is presented. An imine reductase (IRED) from Streptosporangium roseum was identified to catalyze the reaction between 3-cyclopentyl-3-oxopropanenitrile 5 and hydrazine hydrate 2 to produce trace amounts of (R)-3-cyclopentyl-3-hydrazineylpropanenitrile 4. We employed a 2-fold approach to optimize the catalytic performance of this enzyme. First, a transition state analogue (TSA) model was constructed to illuminate the enzyme-substrate interactions. Subsequently, the Enzyme_design and Funclib methods were utilized to predict mutants for experimental evaluation. Through three rounds of site-directed mutagenesis, site saturation mutagenesis, and combinatorial mutagenesis, we obtained mutant M6 with a yield of 98% and an enantiomeric excess (ee) of 99%. This study presents an effective method for constructing a hydrazine derivative via IRED-catalyzed reductive amination of ketone and hydrazine. Furthermore, it provides a general approach for constructing suitable enzymes, starting from nonreactive enzymes and gradually enhancing their catalytic activity through active site modifications.