Protonated Z-scheme CdS-covalent organic framework heterojunction with highly efficient photocatalytic hydrogen evolution.

The low efficiency of photocatalytic hydrogen production from water is mainly suffer from limited light absorption, charge separation and water delivery to the active centers. Herein, an inorganic-organic Z-scheme heterojunction (CdS-COF-Ni) is constructed by in-situ growth of CdS nanosheets on the porphyrin-based covalent organic framework with nickel ions (COF-Ni) in the porphyrin centers. A built-in electric field is formed at the interface, which accelerates the separation and transfer of photogenerated charges. Moreover, through the surface protonation treatment in ascorbic acid (AC) solution, the hydrophilicity of the obtained composite is obviously increased and facilitates the transport of water molecules to the photocatalytic centers. Under the synergistic effect of the interfacial interaction and surface protonation treatment, the photocatalytic hydrogen production rate is optimized to be 18.23 mmol h-1 g-1 without adding any cocatalysts, which is 21 times that of CdS. After a series of photoelectrochemical measurements, in situ X-ray photoelectron spectroscopy (XPS) analysis, and density functional theory (DFT) calculations, it is found that the photocatalytic charge transfer pathway conforms to the Z-scheme mechanism, which not only greatly accelerates the separation and transfer of photogenerated charges, but also retains a high reduction capacity for water splitting. This work offers a good strategy for constructing highly efficient organic-inorganic heterojunctions for water splitting.

Covalent Organic Frameworks Based Electrocatalysts for Two-Electron Oxygen Reduction Reaction: Design Principles, Recent Advances, and Perspective.

Hydrogen peroxide (H2O2) is an environmentally friendly oxidant with a wide range of applications, and the two-electron pathway (2e-) of the oxygen reduction reaction (ORR) for H2O2 production has attracted much attention due to its eco-friendly nature and operational simplicity in contrast to the conventional anthraquinone process. The challenge is to design electrocatalysts with high activity and selectivity and to understand their structure-activity relationship and catalytic mechanism in the ORR process. Covalent organic frameworks (COFs) provide an efficient template for the construction of highly efficient electrocatalysts due to their designable structure, excellent stability, and controllable porosity. This review firstly outlines the design principles of COFs, including the selection of metallic and nonmetallic active sites, the modulation of the electronic structure of the active sites, and the dimensionality modulation of the COFs, to provide guidance for improving the production performance of H2O2. Subsequently, representative results are summarized in terms of both metallic and metal-free sites to follow the latest progress. Moreover, the challenges and perspectives of 2e- ORR electrocatalysts based on COFs are discussed.

Emerging electrospinning platform toward nanoparticle to single atom transformation for steering selectivity in ammonia synthesis.

The rising top-down synthetic methodologies for transition metal single-atom catalysts (SACs) require controlled movement of metal atoms through the substrates; however, their direct transportation towards the ideal carrier remains a huge challenge. Herein, we showed a "top down" strategy for Co nanoparticles (NPs) to Co SA transformation by employing electrospun carbon nanofibers (CNFs) as atom carriers. Under high-temperature conditions, the Co atoms migrate from the surfaces of Co NPs and are then anchored by the surrounding carbon to form a Co-C3O1 coordination structure. The synthesized Co SAs/CNF electrocatalyst exhibits excellent electrocatalytic nitrate reduction reaction (NO3RR) activity with an NH3 yield of 0.79 mmol h-1 cm-2 and Faraday efficiency (FE) of 91.3% at -0.7 V vs. RHE in 0.1 M KNO3 and 0.1 M K2SO4 electrolytes. The in situ electrochemical characterization suggests that the NOH pathway is preferred by Co SAs/CNFs, and *NO hydrogenation and deoxygenation easily occur on Co SAs due to the small adsorption energy between Co SAs and *NO, as calculated by theoretical calculations. It is revealed that a small energy barrier (0.45 eV) for the rate determining step (RDS) ranges from *NO to *NOH and a strong capability for inhibiting hydrogen evolution (HER) significantly promotes the NH3 selectivity and activity of Co SAs/CNFs.

Organic iontronic memristors for artificial synapses and bionic neuromorphic computing.

To tackle the current crisis of Moore's law, a sophisticated strategy entails the development of multistable memristors, bionic artificial synapses, logic circuits and brain-inspired neuromorphic computing. In comparison with conventional electronic systems, iontronic memristors offer greater potential for the manifestation of artificial intelligence and brain-machine interaction. Organic iontronic memristive materials (OIMs), which possess an organic backbone and exhibit stoichiometric ionic states, have emerged as pivotal contenders for the realization of high-performance bionic iontronic memristors. In this review, a comprehensive analysis of the progress and prospects of OIMs is presented, encompassing their inherent advantages, diverse types, synthesis methodologies, and wide-ranging applications in memristive devices. Predictably, the field of OIMs, as a rapidly developing research subject, presents an exciting opportunity for the development of highly efficient neuro-iontronic systems in areas such as in-sensor computing devices, artificial synapses, and human perception.

Volatile guest molecule mediated strategy to convert covalent organic framework into nitrogen, sulfur-doped carbon as metal-free oxygen reduction electrocatalysts.

Covalent organic framework (COF) derived metal-free carbon materials have emerged as promising electrocatalysts for the oxygen reduction reaction (ORR). Herein, a volatile guest molecule mediated-pyrolysis strategy was explored on a designed thiophene-rich and imine-linked COF. Through the modulation of guest mediators (iodine and sulfur), the properties of the as-obtained carbon materials can be well regulated. The optimized nitrogen and sulfur dual-doped carbon electrocatalyst demonstrates remarkable ORR activity with a half-wave potential of 0.87 V and impressive durability, with only an 8% current loss over 21 h. The corresponding assembled zinc-air battery has a comparable power density (60 mW cm-2) to that of the commercial Pt/C. It is proposed that the coexistence of the guest mediators iodine and sulfur in the channels of COFs could prevent the loss of N species. The enhanced N content and N/S ratio are assumed to be responsible for the ORR performance. This study puts forward a novel strategy to prepare COF-derived carbon materials mediated by volatile guest molecules, which may provide new insights into the development of metal-free ORR catalysts.

Dual-phase B-doped FeCoNiCuPd high-entropy alloys for nitrogen electroreduction to ammonia.

Dual-phase B-doped FeCoNiCuPd high-entropy alloy (DP-B-HEA) nanoparticles were synthesized via a strategy involving thermodynamically driven solid-phase diffusion. The DP-B-HEA/CNFs showed an outstanding electrochemical N2 reduction reaction (NRR) performance with an ammonia yield of 24.8 µmol h-1 cm-2 and NH3 faradaic efficiency (FE) of 39.2%. The optimized electronic structures of the HEA resulting from B doping led to the enhanced NRR activity and selectivity.

Clinical features, epidemiology, and treatment of Shwachman-Diamond syndrome: a systematic review.

BACKGROUND: Shwachman-Diamond syndrome (SDS) is an autosomal recessive disease which results in inherited bone marrow failure (IBMF) and is characterized by exocrine pancreatic dysfunction and diverse clinical phenotypes. In the present study, we reviewed the internationally published reports on SDS patients, in order to summarize the clinical features, epidemiology, and treatment of SDS. METHODS: We searched the WangFang and China National Knowledge Infrastructure databases with the keywords "Shwachman-Diamond syndrome," "SDS," "SBDS gene" and "inherited bone marrow failure" for relevant articles published from January 2002 to October 2022. In addition, studies published from January 2002 to October 2022 were searched from the Web of Science, PubMed, and MEDLINE databases, using "Shwachman-diamond syndrome" as the keyword. Finally, one child with SDS treated in Tongji Hospital was also included. RESULTS: The clinical features of 156 patients with SDS were summarized. The three major clinical features of SDS were found to be peripheral blood cytopenia (96.8%), exocrine pancreatic dysfunction (83.3%), and failure to thrive (83.3%). The detection rate of SDS mutations was 94.6% (125/132). Mutations in SBDS, DNAJC21, SRP54, ELF6, and ELF1 have been reported. The male-to-female ratio was approximately 1.3/1. The median age of onset was 0.16 years, but the diagnostic age lagged by a median age of 1.3 years. CONCLUSIONS: Pancreatic exocrine insufficiency and growth failure were common initial symptoms. SDS onset occurred early in childhood, and individual differences were obvious. Comprehensive collection and analysis of case-related data can help clinicians understand the clinical characteristics of SDS, which may improve early diagnosis and promote effective clinical intervention.

Constructing single atom sites on bipyridine covalent organic frameworks for selective electrochemical production of H2O2.

We developed a series of single atom catalysts (SACs) anchored on bipyridine-rich COFs. By tuning the active metal center, the optimal Py-Bpy-COF-Zn shows the highest selectivity of 99.1% and excellent stability toward H2O2 production via oxygen reduction, which can be attributed to the high *OOH dissociation barrier indicated by the theoretical calculations. As a proof of concept, it acts as a cathodic catalyst in a homemade Zn-air battery, together with efficient wastewater treatment.

Solid-phase synthesis of ultra-small CuMo solid solution alloy for efficient electroreduction CO2-to-C2+ production.

We report a fascinating solid-phase synthesis of ultra-small CuMo solid solution alloy nanoclusters (2.1 nm) anchored on electrospun carbon nanofibers (CuMo/CNFs). By tuning the weight ratio of Cu and Mo, the optimized Cu2Mo1/CNFs achieves excellent CO2RR performance with a high faradaic efficiency (FE) of 84.5% for C2+ products and an FEethanol of 75.7%. In situ characterization demonstrates that the Cu2Mo1 alloy can strengthen the adsorption of the crucial intermediate and promote C-C coupling, leading to high selectivity and efficiency for C2+ products.

Competitive Trapping of Single Atoms onto a Metal Carbide Surface.

Controlling atomic adjustment of single-atom catalysts (SACs) can directly change its local configuration, regulate the energy barrier of intermediates, and further optimize reaction pathways. Herein, we report an atom manipulating process to synthesize Ni atoms stabilized on vanadium carbide (NiSA-VC) through a nanofiber-medium thermodynamically driven atomic migration strategy. Experimental and theoretical results systematically reveal the tunable migration pathway of Ni atom from Ni nanoparticles to neighboring N-doped carbon (NC) and finally to metal carbide that was obtained by regulating the competitive adsorption energies between VC and NC for capturing Ni atoms. For CO2-to-CO electroreduction, NiSA-VC exhibits an industrial current density of -180 mA cm-2 at -1.0 V vs reversible hydrogen electrode and the highest Faradaic efficiency for CO production (FECO) of 96.8% at -0.4 V vs RHE in a flow cell. Significant electron transfers occurring in NiSA-VC structures contribute to the activation of CO2, facilitate the reaction free energy, regulate *CO desorption as the rate-determining step, and promote the activity and selectivity. This study provides an understanding on how to design powerful SACs for electrocatalysis.

Ensemble effects of high entropy alloy for boosting alkaline water splitting coupled with urea oxidation.

FeCoNiMoRu/CNFs exhibits a small potential of 1.43 V vs. RHE (100 mA cm-2) and superior stability for 90 h toward urea electro-oxidation (UOR). In situ electrochemical Raman results strongly demonstrate the ensemble effects of the various metal sites on improving the UOR activity by co-stabilizing the important intermediates. This work will open new directions in the application of high-entropy alloys for small molecule oxidation reactions.

Bimetallic palladium-copper nanoplates with optimized d-band center simultaneously boost oxygen reduction activity and methanol tolerance.

The methanol-poisoning of electrocatalysts at the cathodic part of direct methanol fuel cells (DMFCs) can severely degrade the overall efficiency. Therefore, engineering cathodic catalysts with outstanding oxygen reduction activity, and simultaneously, superior methanol tolerance is greatly desired. Herein, bimetallic palladium-copper (PdCu) nanoplates with the optimized d-band center are designed as promising cathodic catalysts for DMFCs. It shows outstanding oxygen reduction activity with a mass activity (MA) of 0.522 A mgPd-1 in alkaline electrolyte, overwhelming the benchmarked commercial Pt/C and Pd/C. Meanwhile, it has prominent stability with only 4.0 % loss in MA after continuous 20 K cycles. More importantly, the PdCu nanoplates are almost inert toward methanol oxidation and show excellent anti-methanol capability. The theoretical calculations reveal that the downshift of d-band center in PdCu nanoplates and the electronic interaction between Pd and Cu atoms could effectively lower the methanol adsorption energy, thus leading to enhanced methanol tolerance. This work highlights the important role of tuning the electronic structure and optimized geometry of electrocatalysts to simultaneously boost their oxygen reduction activity, stability, and methanol tolerance for their future application in DMFCs.

Unraveling the electronegativity-dominated intermediate adsorption on high-entropy alloy electrocatalysts.

High-entropy alloys have received considerable attention in the field of catalysis due to their exceptional properties. However, few studies hitherto focus on the origin of their outstanding performance and the accurate identification of active centers. Herein, we report a conceptual and experimental approach to overcome the limitations of single-element catalysts by designing a FeCoNiXRu (X: Cu, Cr, and Mn) High-entropy alloys system with various active sites that have different adsorption capacities for multiple intermediates. The electronegativity differences between mixed elements in HEA induce significant charge redistribution and create highly active Co and Ru sites with optimized energy barriers for simultaneously stabilizing OH* and H* intermediates, which greatly enhances the efficiency of water dissociation in alkaline conditions. This work provides an in-depth understanding of the interactions between specific active sites and intermediates, which opens up a fascinating direction for breaking scaling relation issues for multistep reactions.

Strain Relaxation in Metal Alloy Catalysts Steers the Product Selectivity of Electrocatalytic CO2 Reduction.

Strain engineering in bimetallic alloy structures is of great interest in electrochemical CO2 reduction reactions (CO2RR), in which it simultaneously improves electrocatalytic activity and product selectivity by optimizing the binding properties of intermediates. However, a reliable synthetic strategy and systematic understanding of the strain effects in the CO2RR are still lacking. Herein, we report a strain relaxation strategy used to determine lattice strains in bimetal MNi alloys (M = Pd, Ag, and Au) and realize an outstanding CO2-to-CO Faradaic efficiency of 96.6% and show the outstanding activity and durability toward a Zn-CO2 battery. Molecular dynamics (MD) simulations predict that the relaxation of strained PdNi alloys (s-PdNi) is correlated with increases in synthesis temperature, and the high temperature activation energy drives complete atomic mixing of multiple metal atoms to allow for regulation of lattice strains. Density functional theory (DFT) calculations reveal that strain relaxation effectively improves CO2RR activity and selectivity by optimizing the formation energies of *COOH and *CO intermediates on s-PdNi alloy surfaces, as also verified by in situ spectroscopic investigations. This approach provides a promising approach for catalyst design, enabling independent optimization of formation energies of reaction intermediates to improve catalytic activity and selectivity simultaneously.

Flexible and recyclable bio-based transient resistive memory enabled by self-healing polyimine membrane.

The recyclable, self-healing and easily-degradable transient electronic technology has aroused tremendous attention in flexible electronic products. However, integrating the above advantages into one single flexible electronic device is still a huge challenge. Herein, we demonstrate a flexible and recyclable bio-based memory device using fish colloid as the resistive switching layer on a polyimine substrate, which affords reliable mechanical and electrical properties under repetitive conformal deformation operation. This flexible bio-based memory device presents potential analog behaviors including memory characteristics and excitatory current response, which undergoes incremental potentiation in conductance under successive electrical pulses. Moreover, this device is expected to greatly alleviate the environmental problems caused by electronic waste. It can be decomposed rapidly in water and well recycled, which is a promising candidate for transient memories and information security. We believe that this study can provide new possibilities to the field of high-performance transient electronics and flexible resistive memory devices.

Conductive metal and covalent organic frameworks for electrocatalysis: design principles, recent progress and perspective.

Metal and covalent organic frameworks (MOFs/COFs) are emerging promising candidates in the field of catalysts due to their porous nature, chemically well-defined active sites and structural diversity. However, they are typically provided with poor electrical conductivity, which is insufficient for them to work as satisfying electrocatalysts. Designing and fabricating MOFs/COFs with high conductivity presents a new avenue towards special electrochemical reactions. This minireview firstly highlighted the origin and design principles of conductive MOFs/COFs for electrocatalysis on the basis of typical charge transfer mechanisms, that is "through space", "extended conjugation" and "through bond". An overview of conductive MOFs/COFs used in the electrocatalytic carbon dioxide reduction reaction (CO2RR), water splitting and the oxygen reduction reaction (ORR) was then made to track the very recent progress. In the final remarks, the present challenges and perspectives for the use of conductive MOFs/COFs as electrocatalysts including their structural optimization, feasible applications and structure-activity correlation are proposed.

Sublayer Stable Fe Dopant in Porous Pd Metallene Boosts Oxygen Reduction Reaction.

Engineering the morphology and electronic properties simultaneously of emerging metallene materials is an effective strategy for enhancing their performance as oxygen reduction reaction (ORR) electrocatalysts. Herein, a highly efficient and stable ORR electrocatalyst, Fe-doped ultrathin porous Pd metallene (Fe-Pd UPM) composed of a few layers of 2D atomic metallene layers, was synthesized using a simple one pot wet-chemical method and characterized. Fe-Pd UPM was measured to have enhanced ORR activity compared to undoped Pd metallene. Fe-Pd UPM exhibits a mass activity of 0.736 A mgPd-1 with a loss of mass activity of only 5.1% after 10 000 cycles at 0.9 V versus the reversible hydrogen electrode (vs RHE) in 0.1 M KOH solution. Density functional theory (DFT) calculations reveal that the stable Fe dopant in the inner atomic layers of Fe-Pd UPM delivers a much smaller overpotential during O* hydrogenation into OH*. The morphology, porous structure, and Fe doping were verified to have enhanced ORR activity. We believe that the rational design of metallene materials with porous structures and interlayer doping is promising for the development of efficient and stable electrocatalysts.

Thermodynamically driven metal diffusion strategy for controlled synthesis of high-entropy alloy electrocatalysts.

We report a thermodynamically driven metal diffusion strategy for the controlled synthesis of high-entropy alloy (HEA) nanocrystals using electrospun carbon nanofibers (CNFs) as nanoreactors. This conceptual pathway is resistant to high temperatures and produces a series of medium-entropy alloy (MEA) and HEA nanocrystals supported on CNFs by adjusting the numbers and kinds of elements. The FeCoNiCrMn/CNFs obtained the lowest overpotential of 345 mV at 50 mA cm-2 compared to MEA. The operando electrochemical Raman results indicate that the enhanced electron transfer from low-electronegativity Fe, Ni, Cr and Mn to the orbit of the Co atom makes Co a local negative charge center, leading to the decrease in absorption energy of OH.

One-dimensional, space-confined, solid-phase growth of the Cu9S5@MoS2 core-shell heterostructure for electrocatalytic hydrogen evolution.

Binary transition metal chalcogenide core-shell nanocrystals are considered the most promising nonprecious metal catalysts for large-scale industrial hydrogen production. Herein, we report a one-dimensional, space-confined, solid-phase strategy for the growth of a Cu9S5@MoS2 core-shell heterostructure by combining electrospinning and chemical vapor deposition methods. The Cu9S5@MoS2 core-shell nanocrystals were synthesized in situ on carbon nanofibers (Cu9S5@MoS2/CNFs) by an S vapor graphitization process. Tuning of the MoS2 shell numbers can be controlled by changing the mass ratio of the Cu and Mo precursors. We experimentally determined the effects of the thickness of the MoS2 shell on the electrocatalytic activity for the hydrogen evolution reaction (HER) in acidic and alkaline solutions. When the mass ratio is 3:1, the Cu9S5@MoS2/CNFs show the fewest MoS2 shells with just 1-2 layers each and exhibit the best HER performance with small overpotentials of 116 mV and 114 mV in acidic and alkaline solutions, respectively, at a current density of 10 mA cm-2. The core shell structures, with their unique Cu-S-Mo nanointerfaces, could enhance the electron transfer and surface area, thus increasing the performance of the HER. This work provides a facile method to design unique core shell assemblies in one-dimensional nanostructures.

One-pot Synthesis of Pd/Azo-polymer as an Efficient Catalyst for 4-Nitrophenol Reduction and Suzuki-Miyaura Coupling Reaction.

The porous polymer matrix with good stability and confined microenvironment is considered as ideal support to stabilize isolated metal centers for catalysis. Herein, we report a "one-pot" method to prepare a kind of palladium complexed with azo porous organic polymer nanospheres (Pd-azo-POPs). The method combines the synthesis of azo-POPs with the reduction of the Pd ion, where azo serves as an anchoring group to limit the growth of Pd. The unique structure is conductive to the formation of a uniform active center and provides improved electron transfer. Pd-azo-POPs-80 exhibits a high catalytic activity and cycling stability both in 4-nitrophenol reduction and Suzuki-Miyaura coupling. The knor for the 4-nitrophenol reduction was 174.7 min-1 mM-1 and the conversion remains above 90% after 6 cycles. Meanwhile, the yield was still up to 94.5% after 5 cycles for the Suzuki-Miyaura coupling reaction of benzene derivatives with I/Br under mild conditions.