Dinickel enzyme evolved to metabolize the pharmaceutical metformin and its implications for wastewater and human microbiomes.

Metformin is the first-line treatment for type II diabetes patients and a pervasive pollutant with more than 180 million kg ingested globally and entering wastewater. The drug's direct mode of action is currently unknown but is linked to effects on gut microbiomes and may involve specific gut microbial reactions to the drug. In wastewater treatment plants, metformin is known to be transformed by microbes to guanylurea, although genes encoding this metabolism had not been elucidated. In the present study, we revealed the function of two genes responsible for metformin decomposition (mfmA and mfmB) found in isolated bacteria from activated sludge. MfmA and MfmB form an active heterocomplex (MfmAB) and are members of the ureohydrolase protein superfamily with binuclear metal-dependent activity. MfmAB is nickel-dependent and catalyzes the hydrolysis of metformin to dimethylamine and guanylurea with a catalytic efficiency (kcat/KM) of 9.6 × 103 M-1s-1 and KM for metformin of 0.82 mM. MfmAB shows preferential activity for metformin, being able to discriminate other close substrates by several orders of magnitude. Crystal structures of MfmAB show coordination of binuclear nickel bound in the active site of the MfmA subunit but not MfmB subunits, indicating that MfmA is the active site for the MfmAB complex. Mutagenesis of residues conserved in the MfmA active site revealed those critical to metformin hydrolase activity and its small substrate binding pocket allowed for modeling of bound metformin. This study characterizes the products of the mfmAB genes identified in wastewater treatment plants on three continents, suggesting that metformin hydrolase is widespread globally in wastewater.

MXene-mediated reconfiguration induces robust nickel-iron catalysts for industrial-grade water oxidation.

Nickel-iron oxy/hydroxides (NiFeOxHy) emerge as an attractive type of electrocatalysts for alkaline water oxidation reaction (WOR), but which encounter a huge challenge in stability, especially at industrial-grade large current density due to uncontrollable Fe leakage. Here, we tailor the Fe coordination by a MXene-mediated reconfiguration strategy for the resultant NiFeOxHy catalyst to alleviate Fe leakage and thus reinforce the WOR stability. The introduction of ultrafine MXene with surface dangling bonds in the electrochemical reconfiguration over Ni-Fe Prussian blue analogue induces the covalent hybridization of NiFeOxHy/MXene, which not only accelerates WOR kinetics but also improves Fe oxidation resistance against segregation. As a result, the NiFeOxHy coupled with MXene exhibits an extraordinary durability at ampere-level current density over 1,000 h for alkaline WOR with an ultralow overpotential of only 307 mV. This work provides a broad avenue and mechanistic insights for the development of nickel-iron catalysts toward industrial applications.

Directional electronic tuning of Ni nanoparticles by interfacial oxygen bridging of support for catalyzing alkaline hydrogen oxidation.

Metallic nickel (Ni) is a promising candidate to substitute Pt-based catalysts for hydrogen oxidation reaction (HOR), but huge challenges still exist in precise modulation of the electronic structure to boost the electrocatalytic performances. Herein, we present the use of single-layer Ti3C2Tx MXene to deliberately tailor the electronic structure of Ni nanoparticles via interfacial oxygen bridges, which affords Ni/Ti3C2Tx electrocatalyst with exceptional performances for HOR in an alkaline medium. Remarkably, it shows a high kinetic current of 16.39 mA cmdisk-2 at the overpotential of 50 mV for HOR [78 and 2.7 times higher than that of metallic Ni and Pt/C (20%), respectively], also with good durability and CO antipoisoning ability (1,000 ppm) that are not available for conventional Pt/C (20%) catalyst. The ultrahigh conductivity of single-layer Ti3C2Tx provides fast transmission of electrons for Ni nanoparticles, of which the uniform and small sizes endow them with high-density active sites. Further, the terminated -O/-OH functional groups on Ti3C2Tx directionally capture electrons from Ni nanoparticles via interfacial Ni-O bridges, leading to obvious electronic polarization. This could enhance the Nids-O2p interaction and weaken Nids-H1s interaction of Ni sites in Ni/Ti3C2Txenabling a suitable H-/OH-binding energy and thus enhancing the HOR activity.

An alcove at the acetyl-CoA synthase nickel active site is required for productive substrate CO binding and anaerobic carbon fixation.

One of the seven natural CO2 fixation pathways, the anaerobic Wood-Ljungdahl pathway (WLP) is unique in generating CO as a metabolic intermediate, operating through organometallic intermediates, and in conserving (versus utilizing) net ATP. The key enzyme in the WLP is acetyl-CoA synthase (ACS), which uses an active site [2Ni-4Fe-4S] cluster (A-cluster), a CO tunnel, and an organometallic (Ni-CO, Ni-methyl, and Ni-acetyl) reaction sequence to generate acetyl-CoA. Here, we reveal that an alcove, which interfaces the tunnel and the A-cluster, is essential for CO2 fixation and autotrophic growth by the WLP. In vitro spectroscopy, kinetics, binding, and in vivo growth experiments reveal that a Phe229A substitution at one wall of the alcove decreases CO affinity thirty-fold and abolishes autotrophic growth; however, a F229W substitution enhances CO binding 80-fold. Our results indicate that the structure of the alcove is exquisitely tuned to concentrate CO near the A-cluster; protect ACS from CO loss during catalysis, provide a haven for inhibitory CO, and stabilize the tetrahedral coordination at the Nip site where CO binds. The directing, concentrating, and protective effects of the alcove explain the inability of F209A to grow autotrophically. The alcove also could help explain current controversies over whether ACS binds CO and methyl through a random or ordered mechanism. Our work redefines what we historically refer to as the metallocenter "active site". The alcove is so crucial for enzymatic function that we propose it is part of the active site. The community should now look for such alcoves in all "gas handling" metalloenzymes.

Cooperative redox and spin activity from three redox congeners of sulfur-bridged iron nitrosyl and nickel dithiolene complexes.

The synthesis of sulfur-bridged Fe-Ni heterobimetallics was inspired by Nature's strategies to "trick" abundant first row transition metals into enabling 2-electron processes: redox-active ligands (including pendant iron-sulfur clusters) and proximal metals. Our design to have redox-active ligands on each metal, NO on iron and dithiolene on nickel, resulted in the observation of unexpectedly intricate physical properties. The metallodithiolate, (NO)Fe(N2S2), reacts with a labile ligand derivative of [NiII(S2C2Ph2)]0, NiDT, yielding the expected S-bridged neutral adduct, FeNi, containing a doublet {Fe(NO)}7. Good reversibility of two redox events of FeNi led to isolation of reduced and oxidized congeners. Characterization by various spectroscopies and single-crystal X-ray diffraction concluded that reduction of the FeNi parent yielded [FeNi]-, a rare example of a high-spin {Fe(NO)}8, described as linear FeII(NO-). Mössbauer data is diagnostic for the redox change at the {Fe(NO)}7/8 site. Oxidation of FeNi generated the 2[FeNi]+⇌[Fe2Ni2]2+ equilibrium in solution; crystallization yields only the [Fe2Ni2]2+ dimer, isolated as PF6- and BArF- salts. The monomer is a spin-coupled diradical between {Fe(NO)}7 and NiDT+, while dimerization couples the two NiDT+ via a Ni2S2 rhomb. Magnetic susceptibility studies on the dimer found a singlet ground state with a thermally accessible triplet excited state responsible for the magnetism at 300 K (χMT = 0.67 emu·K·mol-1, µeff = 2.31 µB), and detectable by parallel-mode EPR spectroscopy at 20 to 50 K. A theoretical model built on an H4 chain explains this unexpected low energy triplet state arising from a combination of anti- and ferromagnetic coupling of a four-radical molecular conglomerate.

A completely precious metal-free alkaline fuel cell with enhanced performance using a carbon-coated nickel anode.

SignificanceWe present a groundbreaking advance in completely nonprecious hydrogen fuel cell technologies achieving a record power density of 200 mW/cm2 with Ni@CNx anode and Co-Mn cathode. The 2-nm CNx coating weakens the O-binding energy, which effectively mitigates the undesirable surface oxidation during hydrogen oxidation reaction (HOR) polarization, leading to a stable fuel cell operation for Ni@CNx over 100 h at 200 mA/cm2, superior to a Ni nanoparticle counterpart. Ni@CNx exhibited a dramatically enhanced tolerance to CO relative to Pt/C, enabling the use of hydrogen gas with trace amounts of CO, critical for practical applications. The complete removal of precious metals in fuel cells lowers the catalyst cost to virtually negligible levels and marks a milestone for practical alkaline fuel cells.

Observation of Three-State Nematicity and Domain Evolution in Atomically Thin Antiferromagnetic NiPS3.

Nickel phosphorus trisulfide (NiPS3), a van der Waals 2D antiferromagnet, has received significant interest for its intriguing properties in recent years. However, despite its fundamental importance in the physics of low-dimensional magnetism and promising potential for technological applications, the study of magnetic domains in NiPS3 down to an atomically thin state is still lacking. Here, we report the layer-dependent magnetic characteristics and magnetic domains in NiPS3 by employing linear dichroism spectroscopy, polarized microscopy, spin-correlated photoluminescence, and Raman spectroscopy. Our results reveal the existence of the paramagnetic-to-antiferromagnetic phase transition in bulk to bilayer NiPS3 and provide evidence of the role of stronger spin fluctuations in thin NiPS3. Furthermore, our study identifies three distinct antiferromagnetic domains within atomically thin NiPS3 and captures the thermally activated domain evolution. Our findings provide crucial insights for the development of antiferromagnetic spintronics and related technologies.

One-Step Electrochemically Prepared Bionic Hierarchical Nickel Black@Graphene Composite Membrane for Desalination by Solar-Thermal Energy Conversion.

Ingenious microstructure construction and appropriate composition selection are effective strategies for achieving enhanced performance of photothermal materials. Herein, a broccoli-like hierarchical nickel black@graphene (Ni@Gr) membrane for solar-driven desalination was prepared by a one-step electrochemical method, which was carried out simultaneously with the electrochemical exfoliation of graphene and the co-deposition of Ni@Gr material. The bionic hierarchical structure and the chemical composition of the Ni@Gr membrane increased the sunlight absorption (90.36%) by the light-trapping effect and the introduction of graphene. The Ni@Gr membrane achieved high evaporation rates of 2.05 and 1.16 kg m-2 h-1 under simulated (1 sun) and outdoor sunlight conditions, respectively. The superhydrophilicity and the hierarchical structure of the Ni@Gr membrane jointly reduced the evaporation enthalpy (1343.6 kJ/kg), which was beneficial to break the theoretical limit of the evaporation rate (1.47 kg m-2 h-1). This work encourages the application of bionic metal-carbon composite photothermal materials in solar water evaporation.

Simultaneous Identification of Major Thyroid Hormones by a Nickel Immobilized Biological Nanopore.

Thyroid hormones (THs) are a variety of iodine-containing hormones that demonstrate critical physiological impacts on cellular activities. The assessment of thyroid function and the diagnosis of thyroid disorders require accurate measurement of TH levels. However, largely due to their structural similarities, the simultaneous discrimination of different THs is challenging. Nanopores, single-molecule sensors with a high resolution, are suitable for this task. In this paper, a hetero-octameric Mycobacterium smegmatis porin A (MspA) nanopore containing a single nickel ion immobilized to the pore constriction has enabled simultaneous identification of five representative THs including l-thyroxine (T4), 3,3',5-triiodo-l-thyronine (T3), 3,3',5'-triiodo-l-thyronine (rT3), 3,5-diiodo-l-thyronine (3,5-T2) and 3,3'-diiodo-l-thyronine (3,3'-T2). To automate event classification and avoid human bias, a machine learning algorithm was also developed, reporting an accuracy of 99.0%. This sensing strategy is also applied in the analysis of TH in a real human serum environment, suggesting its potential use in a clinical diagnosis.

Proteus mirabilis UreR coordinates cellular functions required for urease activity.

A hallmark of Proteus mirabilis infection of the urinary tract is the formation of stones. The ability to induce urinary stone formation requires urease, a nickel metalloenzyme that hydrolyzes urea. This reaction produces ammonia as a byproduct, which can serve as a nitrogen source and weak base that raises the local pH. The resulting alkalinity induces the precipitation of ions to form stones. Transcriptional regulator UreR activates expression of urease genes in a urea-dependent manner. Thus, urease genes are highly expressed in the urinary tract where urea is abundant. Production of mature urease also requires the import of nickel into the cytoplasm and its incorporation into the urease apoenzyme. Urease accessory proteins primarily acquire nickel from one of two nickel transporters and facilitate incorporation of nickel to form mature urease. In this study, we performed a comprehensive RNA-seq to define the P. mirabilis urea-induced transcriptome as well as the UreR regulon. We identified UreR as the first defined regulator of nickel transport in P. mirabilis. We also offer evidence for the direct regulation of the Ynt nickel transporter by UreR. Using bioinformatics, we identified UreR-regulated urease loci in 15 Morganellaceae family species across three genera. Additionally, we located two mobilized UreR-regulated urease loci that also encode the ynt transporter, implying that UreR regulation of nickel transport is a conserved regulatory relationship. Our study demonstrates that UreR specifically regulates genes required to produce mature urease, an essential virulence factor for P. mirabilis uropathogenesis. IMPORTANCE: Catheter-associated urinary tract infections (CAUTIs) account for over 40% of acute nosocomial infections in the USA and generate $340 million in healthcare costs annually. A major causative agent of CAUTIs is Proteus mirabilis, an understudied Gram-negative pathogen noted for its ability to form urinary stones via the activity of urease. Urease mutants cannot induce stones and are attenuated in a murine UTI model, indicating this enzyme is essential to P. mirabilis pathogenesis. Transcriptional regulation of urease genes by UreR is well established; here, we expand the UreR regulon to include regulation of nickel import, a function required to produce mature urease. Furthermore, we reflect on the role of urea catalysis in P. mirabilis metabolism and provide evidence for its importance.

Polychrome labeling reveals skeletal triradiate and elongation dynamics and abnormalities in patterning cue-perturbed embryos.

The larval skeleton of the sea urchin Lytechinus variegatus is an ideal model system for studying skeletal patterning; however, our understanding of the etiology of skeletal patterning in sea urchin larvae is limited due to the lack of approaches to live-image skeleton formation. Calcium-binding fluorochromes have been used to study the temporal dynamics of bone growth and healing. To date, only calcein green has been used in sea urchin larvae to fluorescently label the larval skeleton. Here, we optimize labeling protocols for two additional calcium-binding fluorochromes: xylenol orange and calcein blue- and demonstrate that these fluorochromes can be used individually or in nested pulse-chase experiments to understand the temporal dynamics of skeletogenesis and patterning. Using a pulse-chase approach, we show that the initiation of skeletogenesis begins around 15 â€‹h post fertilization. We also assess the timing of triradiate formation in embryos treated with a range of patterning perturbagens and demonstrate that triradiate formation is delayed and asynchronous in embryos ventralized via treatment with either nickel or chlorate. Finally, we measure the extent of fluorochrome incorporation in triple-labeled embryos to determine the elongation rate of numerous skeletal elements throughout early skeletal patterning and compare this to the rate of skeletal growth in embryos treated with axitinib to inhibit VEGFR. We find that skeletal elements elongate much more slowly in axitinib-treated embryos, and that axitinib treatment is sufficient to induce abnormal orientation of the triradiates.

Atypical genotoxicity of carcinogenic nickel(II): Linkage to dNTP biosynthesis, DNA-incorporated rNMPs, and impaired repair of TOP1-DNA crosslinks.

Cancer is a genetic disease requiring multiple mutations for its development. However, many carcinogens are DNA-unreactive and nonmutagenic and consequently described as nongenotoxic. One of such carcinogens is nickel, a global environmental pollutant abundantly emitted by burning of coal. We investigated activation of DNA damage responses by Ni and identified this metal as a replication stressor. Genotoxic stress markers indicated the accumulation of ssDNA and stalled replication forks, and Ni-treated cells were dependent on ATR for suppression of DNA damage and long-term survival. Replication stress by Ni resulted from destabilization of RRM1 and RRM2 subunits of ribonucleotide reductase and the resulting deficiency in dNTPs. Ni also increased DNA incorporation of rNMPs (detected by a specific fluorescent assay) and strongly enhanced their genotoxicity as a result of repressed repair of TOP1-DNA protein crosslinks (TOP1-DPC). The DPC-trap assay found severely impaired SUMOylation and K48-polyubiquitination of DNA-crosslinked TOP1 due to downregulation of specific enzymes. Our findings identified Ni as the human carcinogen inducing genome instability via DNA-embedded ribonucleotides and accumulation of TOP1-DPC which are carcinogenic abnormalities with poor detectability by the standard mutagenicity tests. The discovered mechanisms for Ni could also play a role in genotoxicity of other protein-reactive carcinogens.

Mechanistic insights into the nickel-dependent allosteric response of the Helicobacter pylori NikR transcription factor.

In Helicobacter pylori, the nickel-responsive NikR transcription factor plays a key role in regulating intracellular nickel concentrations, which is an essential process for survival of this pathogen in the acidic human stomach. Nickel binding to H. pylori NikR (HpNikR) allosterically activates DNA binding to target promoters encoding genes involved in nickel homeostasis and acid adaptation, to either activate or repress their transcription. We previously showed that HpNikR adopts an equilibrium between an open conformation and DNA-binding competent cis and trans states. Nickel binding slows down conformational exchange between these states and shifts the equilibrium toward the binding-competent states. The protein then becomes stabilized in a cis conformation upon binding the ureA promoter. Here, we investigate how nickel binding creates this response and how it is transmitted to the DNA-binding domains. Through mutagenesis, DNA-binding studies, and computational methods, the allosteric response to nickel was found to be propagated from the nickel-binding sites to the DNA-binding domains via the ß-sheets of the metal-binding domain and a network of residues at the inter-domain interface. Our computational results suggest that nickel binding increases protein rigidity to slow down the conformational exchange. A thymine base in the ureA promoter sequence, known to be critical for high affinity DNA binding by HpNikR, was also found to be important for the allosteric response, while a modified version of this promoter further highlighted the importance of the DNA sequence in modulating the response. Collectively, our results provide insights into regulation of a key protein for H. pylori survival.

Comparative genomic analysis of nickel homeostasis in cable bacteria.

BACKGROUND: Cable bacteria are filamentous members of the Desulfobulbaceae family that are capable of performing centimetre­scale electron transport in marine and freshwater sediments. This long­distance electron transport is mediated by a network of parallel conductive fibres embedded in the cell envelope. This fibre network efficiently transports electrical currents along the entire length of the centimetre­long filament. Recent analyses show that these fibres consist of metalloproteins that harbour a novel nickel­containing cofactor, which indicates that cable bacteria have evolved a unique form of biological electron transport. This nickel­dependent conduction mechanism suggests that cable bacteria are strongly dependent on nickel as a biosynthetic resource. Here, we performed a comprehensive comparative genomic analysis of the genes linked to nickel homeostasis. We compared the genome­encoded adaptation to nickel of cable bacteria to related members of the Desulfobulbaceae family and other members of the Desulfobulbales order. RESULTS: Presently, four closed genomes are available for the monophyletic cable bacteria clade that consists of the genera Candidatus Electrothrix and Candidatus Electronema. To increase the phylogenomic coverage, we additionally generated two closed genomes of cable bacteria: Candidatus Electrothrix gigas strain HY10­6 and Candidatus Electrothrix antwerpensis strain GW3­4, which are the first closed genomes of their respective species. Nickel homeostasis genes were identified in a database of 38 cable bacteria genomes (including 6 closed genomes). Gene prevalence was compared to 19 genomes of related strains, residing within the Desulfobulbales order but outside of the cable bacteria clade, revealing several genome­encoded adaptations to nickel homeostasis in cable bacteria. Phylogenetic analysis indicates that nickel importers, nickel­binding enzymes and nickel chaperones of cable bacteria are affiliated to organisms outside the Desulfobulbaceae family, with several proteins showing affiliation to organisms outside of the Desulfobacterota phylum. Conspicuously, cable bacteria encode a unique periplasmic nickel export protein RcnA, which possesses a putative cytoplasmic histidine­rich loop that has been largely expanded compared to RcnA homologs in other organisms. CONCLUSION: Cable bacteria genomes show a clear genetic adaptation for nickel utilization when compared to closely related genera. This fully aligns with the nickel­dependent conduction mechanism that is uniquely found in cable bacteria.

Exploring the synergistic effects of indole acetic acid (IAA) and compost in the phytostabilization of nickel (Ni) in cauliflower rhizosphere.

Heavy metals (HMs) contamination, owing to their potential links to various chronic diseases, poses a global threat to agriculture, environment, and human health. Nickel (Ni) is an essential element however, at higher concentration, it is highly phytotoxic, and affects major plant functions. Beneficial roles of plant growth regulators (PGRs) and organic amendments in mitigating the adverse impacts of HM on plant growth has gained the attention of scientific community worldwide. Here, we performed a greenhouse study to investigate the effect of indole-3-acetic acid (IAA @ 10- 5 M) and compost (1% w/w) individually and in combination in sustaining cauliflower growth and yield under Ni stress. In our results, combined application proved significantly better than individual applications in alleviating the adverse effects of Ni on cauliflower as it increased various plant attributes such as plant height (49%), root length (76%), curd height and diameter (68 and 134%), leaf area (75%), transpiration rate (36%), stomatal conductance (104%), water use efficiency (143%), flavonoid and phenolic contents (212 and 133%), soluble sugars and protein contents (202 and 199%), SPAD value (78%), chlorophyll 'a and b' (219 and 208%), carotenoid (335%), and NPK uptake (191, 79 and 92%) as compared to the control. Co-application of IAA and compost reduced Ni-induced electrolyte leakage (64%) and improved the antioxidant activities, including APX (55%), CAT (30%), SOD (43%), POD (55%), while reducing MDA and H2O2 contents (77 and 52%) compared to the control. The combined application also reduced Ni uptake in roots, shoots, and curd by 51, 78 and 72% respectively along with an increased relative production index (78%) as compared to the control. Hence, synergistic application of IAA and compost can mitigate Ni induced adverse impacts on cauliflower growth by immobilizing it in the soil.

Temperature-Dependent Modulation of Short-Wave-Infrared Light Transparency Based on Associated Structures of a Liquescent Nickel(III) Complex.

A liquescent bis(malononitriledithiolato)nickel(III) complex with a bis(methoxyethyl)imidazolium cation, 1[Ni(mnt)2 ], exhibits three-stage thermochromic modulation of transparency/absorption in the short-wave-infrared (SWIR) region (1000-2500 nm), driven by associated structural changes. Upon heating, the electronic spectra of 1[Ni(mnt)2 ] in the SWIR region shift to shorter wavelengths accompanying with the solid-liquid phase transition at 76 °C. Further heating to over 109 °C induces a second transition of the electronic spectra, characterized by a blue-shift of the SWIR absorption in the liquid phase. The results of temperature-dependent electronic spectra and magnetic susceptibility indicated that the thermochromic changes can be attributed to the two-step dissociation of the associated structures of [Ni(mnt)2 ]- , occurring during the solid-liquid phase transition and the shift of dimer-monomer equilibrium in the liquid state. These changes can be visualized using an SWIR imaging camera under appropriate SWIR lights.

Dual-Functional Ru/Ni-B-P Electrocatalyst Toward Accelerated Water Electrolysis and High-Stability.

Development of advanced electrocatalysts for the green hydrogen production by water electrolysis is an important task to reduce the climate and environmental issues as well as to meet the future energy demands. Herein, Ru/Ni-B-P sphere electrocatalyst is demonstrated by a combination of hydrothermal and soaking approaches, meeting the industrial requirement of low cell voltage with stable high-current operation. The Ru/Ni-B-P sphere catalyst demonstrates low overpotentials of 191 and 350 mV at 300 mA cm-2 with stable high current operation, ranking it as one of the best oxygen evolution reaction (OER) electrocatalysts. The bifunctional 2-E system demonstrates a low cell voltage of 2.49 V at 2000 mA cm-2 in 6 m KOH at 60 °C of harsh industrial operation condition. It also demonstrates outstanding stability with continuous 120 h (5 days) CA operation at 1000 mA cm-2. Further, the hybrid configuration of Ru/Ni-B-P || Pt/C being paired with the conventional benchmark electrode demonstrates a record low 2-E cell voltage of 2.40 V at 2000 mA cm-2 in 6 m KOH and excellent stability at high current of 1500 mA cm-2 under industrial operational condition.

Carbonyl-Supported Coordination in Imidazolates: A Platform for Designing Porous Nickel-Based ZIFs as Heterogeneous Catalysts.

Zeolitic imidazolate frameworks (ZIFs) are a subclass of metal-organic framework that have attracted considerable attention as potential functional materials due to their high chemical stability and ease of synthesis. ZIFs are usually composed of zinc ions coordinated with imidazole linkers, with some other transition metals, such as Cu(II) and Co(II), also showing potential as ZIF-forming cations. Despite the importance of nickel in catalysis, no Ni-based ZIF with permanent porosity is yet reported. It is found that the presence and arrangement of the carbonyl functional groups on the imidazole linker play a crucial role in completing the preferred octahedral coordination of nickel, revealing a promising platform for the rational design of Ni-based ZIFs for a wide range of catalytic applications. Herein, the synthesis of the first Ni-based ZIFs is reported and their high potential as heterogeneous catalysts for Suzuki-Miyaura cross-coupling C─C bond forming reactions is demonstrated.

Promoting OH- Adsorption and Diffusion Enables Ultrahigh Capacity and Rate Capability of Nickel Sulfide Cathode for Aqueous Alkaline Zn-Based Batteries.

Aqueous alkaline Zn-based batteries (AAZBs) possess great promise for large-scale applications thanks to their higher discharging plateau and unique reaction mechanism. However, the capacity and rate capability of Ni-based cathodes are still unsatisfactory due to their insufficient OH- adsorption and diffusion ability. Herein, heterostructured Ni3 S2 /Ni(OH)2 nanosheets with outstanding electrochemical performance are synthesized via a facile chemical etching strategy. The heterostructured Ni3 S2 /Ni(OH)2 nanosheet cathode shows significantly increased capacity and rate capability due to its boosted OH- adsorption and diffusion ability compared to Ni3 S2 . Consequently, the assembled Zn//Ni3 S2 /Ni(OH)2 cell can deliver an ultrahigh capacity of 2.26 mAh cm-2 , an excellent rate performance (0.91 mAh cm-2 at 100 mA cm-2 ) and a satisfying cycling stability (1.01 mAh cm-2 at 20 mA cm-2 after 500 cycles). Moreover, a prominent energy density of 3.86 mWh cm-2 is obtained, which exceeds the majority of recently reported AAZBs. This work is expected to provide a new modification direction for developing high-performance nickel sulfide cathode for AAZBs.

Multifunctional Catalytic Hierarchical Interfaces of Ni12 P5 -Ni2 P Porous Nanosheets Enabled Both Sulfides Reaction Promotion and Li-Dendrite Suppression for High-Performance Li-S Full Batteries.

The development of lithium-sulfur (Li-S) batteries is very promising and yet faces the issues of hindered polysulfides conversion and Li dendrite growth. Different from using different materials strategies to overcome these two types of problems, here multifunctional catalytic hierarchical interfaces of Ni12 P5 -Ni2 P porous nanosheets formed by Ni2 P partially in situ converted from Ni12 P5 are proposed. The unique electronic structure in the interface endows Ni12 P5 -Ni2 P effective electrocatalysis effect toward both sulfides' reduction and oxidation through reducing Gibbs free energies, indicating a bidirectional conversion acceleration. Importantly, Ni12 P5 -Ni2 P porous nanosheets with hierarchical interfaces also reduced the Li nucleation energy barrier, and a dendrite-free Li deposition is realized during the overall Li deposition and stripping steps. To this end, Ni12 P5 -Ni2 P decorated carbon nanotube/S cathode showing a high capacity of over 1500 mAh g-1 , and a high rate capability of 8 C. Moreover, the coin full cell delivered a high capacity of 1345 mAh g-1 at 0.2 C and the pouch full cell delivered a high capacity of 1114 mAh g-1 at 0.2 C with high electrochemical stability during 180° bending. This work inspires the exploration of hierarchical structures of 2D materials with catalytically active interfaces to improve the electrochemistry of Li-S full battery.