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1.
World J Clin Cases ; 12(17): 3221-3225, 2024 Jun 16.
Article in English | MEDLINE | ID: mdl-38898866

ABSTRACT

BACKGROUND: An intrauterine device (IUD) is a contraceptive device placed in the uterine cavity and is a common contraceptive method for Chinese women. However, an IUD may cause complications due to placement time, intrauterine pressure and other factors. Ectopic IUDs are among the most serious complications. Ectopic IUDs are common in the myometrium and periuterine organs, and there are few reports of ectopic IUDs in the urinary bladder, especially in the anterior wall. CASE SUMMARY: A 52-year-old woman was hospitalized due to a urinary bladder foreign body found via abdominal ultrasound and computed tomography (CT) examination. The patient had a 2-year history of recurrent abdominal distension and lower abdominal pain, accompanied by frequent urination, urgency, dysuria and other discomfort. Ultrasound examination revealed foreign bodies in the bladder cavity, with calculus on the surface of the foreign bodies. CT revealed a circular foreign body on the anterior wall of the urinary bladder, suggesting the possibility of an ectopic IUD. After laparoscopic exploration, an annular IUD was found in the anterior wall of urinary bladder, and an oval calculus with a diameter of approximately 2 cm was attached to the surface of the bladder cavity. The IUD and calculus were successfully and completely removed. The patient recovered well after surgery. CONCLUSION: Abdominal ultrasound and CT are effective methods for detecting ectopic IUDs. The IUD is located in the urinary bladder and requires early surgical treatment. The choice of surgical method is determined by comprehensively considering the depth of the IUD in the bladder muscle layer, the situation of complicated calculus, the situation of intravesical inflammation and medical technology and equipment.

2.
Small ; : e2311509, 2024 Apr 08.
Article in English | MEDLINE | ID: mdl-38587968

ABSTRACT

Developing robust non-platinum electrocatalysts with multifunctional active sites for pH-universal hydrogen evolution reaction (HER) is crucial for scalable hydrogen production through electrochemical water splitting. Here ultra-small ruthenium-nickel alloy nanoparticles steadily anchored on reduced graphene oxide papers (Ru-Ni/rGOPs) as versatile electrocatalytic materials for acidic and alkaline HER are reported. These Ru-Ni alloy nanoparticles serve as pH self-adaptive electroactive species by making use of in situ surface reconstruction, where surface Ni atoms are hydroxylated to produce bifunctional active sites of Ru-Ni(OH)2 for alkaline HER, and selectively etched to form monometallic Ru active sites for acidic HER, respectively. Owing to the presence of Ru-Ni(OH)2 multi-site surface, which not only accelerates water dissociation to generate reactive hydrogen intermediates but also facilitates their recombination into hydrogen molecules, the self-supported Ru90Ni10/rGOP hybrid electrode only takes overpotential of as low as ≈106 mV to deliver current density of 1000 mA cm-2, and maintains exceptional stability for over 1000 h in 1 m KOH. While in 0.5 m H2SO4, the Ru90Ni10/rGOP hybrid electrode exhibits acidic HER catalytic behavior comparable to commercially available Pt/C catalyst due to the formation of monometallic Ru shell. These electrochemical behaviors outperform some of the best Ru-based catalysts and make it attractive alternative to Pt-based catalysts toward highly efficient HER.

3.
Adv Mater ; 36(26): e2403803, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38598181

ABSTRACT

Aqueous zinc-ion batteries are attractive post-lithium battery technologies for grid-scale energy storage because of their inherent safety, low cost and high theoretical capacity. However, their practical implementation in wide-temperature surroundings persistently confronts irregular zinc electrodeposits and parasitic side reactions on metal anode, which leads to poor rechargeability, low Coulombic efficiency and short lifespan. Here, this work reports lamellar nanoporous Cu/Al2Cu heterostructure electrode as a promising anode host material to regulate high-efficiency and dendrite-free zinc electrodeposition and stripping for wide-temperatures aqueous zinc-ion batteries. In this unique electrode, the interconnective Cu/Al2Cu heterostructure ligaments not only facilitate fast electron transfer but work as highly zincophilic sites for zinc nucleation and deposition by virtue of local galvanic couples while the interpenetrative lamellar channels serving as mass transport pathways. As a result, it exhibits exceptional zinc plating/stripping behaviors in aqueous hybrid electrolyte of diethylene glycol dimethyl ether and zinc trifluoromethanesulfonate at wide temperatures ranging from 25 to -30 °C, with ultralow voltage polarizations at various current densities and ultralong lifespan of >4000 h. The outstanding electrochemical properties enlist full cell of zinc-ion batteries constructed with nanoporous Cu/Al2Cu and ZnxV2O5/C to maintain high capacity and excellent stability for >5000 cycles at 25 and -30 °C.

4.
Angew Chem Int Ed Engl ; 63(18): e202402327, 2024 Apr 24.
Article in English | MEDLINE | ID: mdl-38467561

ABSTRACT

Metallic zinc is a promising anode material for rechargeable aqueous multivalent metal-ion batteries due to its high capacity and low cost. However, the practical use is always beset by severe dendrite growth and parasitic side reactions occurring at anode/electrolyte interface. Here we demonstrate dynamic molecular interphases caused by trace dual electrolyte additives of D-mannose and sodium lignosulfonate for ultralong-lifespan and dendrite-free zinc anode. Triggered by plating and stripping electric fields, the D-mannose and lignosulfonate species are alternately and reversibly (de-)adsorbed on Zn metal, respectively, to accelerate Zn2+ transportation for uniform Zn nucleation and deposition and inhibit side reactions for high Coulombic efficiency. As a result, Zn anode in such dual-additive electrolyte exhibits highly reversible and dendrite-free Zn stripping/plating behaviors for >6400 hours at 1 mA cm-2, which enables long-term cycling stability of Zn||ZnxMnO2 full cell for more than 2000 cycles.

5.
Small ; 20(26): e2310722, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38229525

ABSTRACT

Aqueous aluminum-ion batteries are attractive post-lithium battery technologies for large-scale energy storage in virtue of abundant and low-cost Al metal anode offering ultrahigh capacity via a three-electron redox reaction. However, state-of-the-art cathode materials are of low practical capacity, poor rate capability, and inadequate cycle life, substantially impeding their practical use. Here layered manganese oxide that is pre-intercalated with benzoquinone-coordinated aluminum ions (BQ-AlxMnO2) as a high-performance cathode material of rechargeable aqueous aluminum-ion batteries is reported. The coordination of benzoquinone with aluminum ions not only extends interlayer spacing of layered MnO2 framework but reduces the effective charge of trivalent aluminum ions to diminish their electrostatic interactions, substantially boosting intercalation/deintercalation kinetics of guest aluminum ions and improving structural reversibility and stability. When coupled with Zn50Al50 alloy anode in 2 m Al(OTf)3 aqueous electrolyte, the BQ-AlxMnO2 exhibits superior rate capability and cycling stability. At 1 A g-1, the specific capacity of BQ-AlxMnO2 reaches ≈300 mAh g-1 and retains ≈90% of the initial value for more than 800 cycles, along with the Coulombic efficiency of as high as ≈99%, outperforming the AlxMnO2 without BQ co-incorporation.

6.
Nano Lett ; 23(11): 5307-5316, 2023 Jun 14.
Article in English | MEDLINE | ID: mdl-37276017

ABSTRACT

The dissolution of transition metal ions causes the notorious peeling of active substances and attenuates electrochemical capacity. Frustrated by the ceaseless task of pushing a boulder up a mountain, Sisyphus of the Greek myth yearned for a treasure to be unearthed that could bolster his efforts. Inspirationally, by using ferricyanide ions (Fe(CN)63-) in an electrolyte as a driving force and taking advantage of the fast nucleation rate of copper hexacyanoferrate (CuHCF), we successfully reversed the dissolution of Fe and Cu ions that typically occurs during cycling. The capacity retention increased from 5.7% to 99.4% at 0.5 A g-1 after 10,000 cycles, and extreme stability of 99.8% at 1 A g-1 after 40,000 cycles was achieved. Fe(CN)63- enables atom-by-atom substitution during the electrochemical process, enhancing conductivity and reducing volume change. Moreover, we demonstrate that this approach is applicable to various aqueous batteries (i.e., NH4+, Li+, Na+, K+, Mg2+, Ca2+, and Al3+).

7.
Nat Commun ; 14(1): 2319, 2023 Apr 22.
Article in English | MEDLINE | ID: mdl-37087491

ABSTRACT

Potassium oxide (K2O) is used as a promotor in industrial ammonia synthesis, although metallic potassium (K) is better in theory. The reason K2O is used is because metallic K, which volatilizes around 400 °C, separates from the catalyst in the harsh ammonia synthesis conditions of the Haber-Bosch process. To maximize the efficiency of ammonia synthesis, using metallic K with low temperature reaction below 400 °C is prerequisite. Here, we synthesize ammonia using metallic K and Fe as a catalyst via mechanochemical process near ambient conditions (45 °C, 1 bar). The final ammonia concentration reaches as high as 94.5 vol%, which was extraordinarily higher than that of the Haber-Bosch process (25.0 vol%, 450 °C, 200 bar) and our previous work (82.5 vol%, 45 °C, 1 bar).

8.
Nat Commun ; 14(1): 1811, 2023 Mar 31.
Article in English | MEDLINE | ID: mdl-37002220

ABSTRACT

Developing robust nonprecious-metal electrocatalysts with high activity towards sluggish oxygen-evolution reaction is paramount for large-scale hydrogen production via electrochemical water splitting. Here we report that self-supported laminate composite electrodes composed of alternating nanoporous bimetallic iron-cobalt alloy/oxyhydroxide and cerium oxynitride (FeCo/CeO2-xNx) heterolamellas hold great promise as highly efficient electrocatalysts for alkaline oxygen-evolution reaction. By virtue of three-dimensional nanoporous architecture to offer abundant and accessible electroactive CoFeOOH/CeO2-xNx heterostructure interfaces through facilitating electron transfer and mass transport, nanoporous FeCo/CeO2-xNx composite electrodes exhibit superior oxygen-evolution electrocatalysis in 1 M KOH, with ultralow Tafel slope of ~33 mV dec-1. At overpotential of as low as 360 mV, they reach >3900 mA cm-2 and retain exceptional stability at ~1900 mA cm-2 for >1000 h, outperforming commercial RuO2 and some representative oxygen-evolution-reaction catalysts recently reported. These electrochemical properties make them attractive candidates as oxygen-evolution-reaction electrocatalysts in electrolysis of water for large-scale hydrogen generation.

9.
Bioresour Technol ; 373: 128751, 2023 Apr.
Article in English | MEDLINE | ID: mdl-36805829

ABSTRACT

To elevate the efficiency of acetone-butanol-ethanol (ABE) fermentation by the wild-type strain WK, an optimal co-utilization system (20 mM Fe3+ and 5 g/L butyrate) was established to bring about a 22.22% increment in the yield of ABE mixtures with a significantly enhanced productivity (0.32 g/L/h). With the heterologous introduction of the secondary alcohol dehydrogenase encoded gene (adh), more than 95% of acetone was eliminated to convert 4.5 g/L isopropanol with corresponding increased butanol and ethanol production by 21.08% and 65.45% in the modified strain WK::adh. Under the optimal condition, strain WK::adh was capable of producing a total of 25.46 g/L IBE biosolvents with an enhanced productivity of 0.35 g/L/h by 45.83% over the original conditions. This work for the first time successfully established a synergetic system of co-utilizing Fe(III) and butyrate to demonstrate a feasible and efficient manner for generating the value-added biofuels through the metabolically engineered solventogenic clostridial strain.


Subject(s)
2-Propanol , Butanols , Fermentation , Ferric Compounds , Acetone , Butyrates , 1-Butanol , Clostridium/genetics , Ethanol
10.
Sci Total Environ ; 861: 160559, 2023 Feb 25.
Article in English | MEDLINE | ID: mdl-36574546

ABSTRACT

With the determination of the Leloir pathway in a solventogenic wild-type strain WK through the transcriptional analysis, two pivotal genes (galK and galT) were systematically co-expressed to demonstrate a significantly enhanced galactose utilization for butanol production with the elimination of carbon catabolite repression (CCR). The gene-modified strain WK-Gal-4 could effectively co-utilize galactose and glucose by directly using an ultrasonication-assisted butyric acid-pretreated Gelidium amansii hydrolysate (BAU) as the substrate, exhibiting the optimal sugar consumption and butanol production from BAU of 20.31 g/L and 7.8 g/L with an increment by 62.35 % and 61.49 % over that by strain WK, respectively. This work for the first time develops a feasible approach to utilizing red algal biomass for butanol fermentation through exploring the metabolic regulation of carbohydrate catabolism, also offering a novel route to develop the future biorefinery using the cost-effective and sustainable marine feedstocks.


Subject(s)
Catabolite Repression , Seaweed , Butanols/metabolism , Galactose , Seaweed/metabolism , Clostridium , 1-Butanol/metabolism , Glucose/metabolism , Fermentation
11.
Article in Chinese | WPRIM (Western Pacific) | ID: wpr-981619

ABSTRACT

OBJECTIVE@#To investigate the feasibility and effectiveness of fascial tissue flaps and skin flaps with layered sutures for repairing wounds after excision of sacrococcygeal pilonidal sinus.@*METHODS@#Between March 2019 and August 2022, 9 patients with sacrococcygeal pilonidal sinus were admitted, including 7 males and 2 females with an average age of 29.4 years (range, 17-53 years). The disease duration ranged from 1 to 36 months, with a median of 6 months. There were 7 cases with obesity and dense hair, 3 cases with infection, and 2 cases with positive bacterial culture of sinus secretion. The wound area after excision ranged from 3 cm×3 cm to 8 cm×4 cm, with a depth of 3-5 cm, reaching the perianal or caudal bone; there were 2 cases with perianal abscess formation and 1 case with caudal bone inflammatory edema. Enlarged resection was performed during operation, and the fascial tissue flap and skin flap were designed and excised at both left and right sides of the buttock, ranging from 3.0 cm×1.5 cm to 8.0 cm×2.0 cm. A cross drainage tube was placed at the bottom of the wound, and the fascial tissue flap and skin flap were advanced and sutured in three layers, namely, 8-string sutures in the fascial layer, barbed wire reduction sutures in the dermis, and interrupted skin sutures.@*RESULTS@#All 9 patients were followed up 3-36 months, with an average of 12 months. All incisions healed by first intention, and no complication such as incisional dehiscence or infection in the operative area occurred. There was no recurrence of sinus tracts, the shape of gluteal sulcus was satisfactory, both sides of buttocks were symmetrical, local incision scar was concealed, and the shape disruption was minimal.@*CONCLUSION@#Fascial tissue flaps and skin flaps with layered sutures for repairing wounds after excision of sacrococcygeal pilonidal sinus can effectively fill the cavity and reduce the incidence of poor incision healing, with the advantages of small trauma and simple operation.


Subject(s)
Male , Female , Humans , Adult , Pilonidal Sinus/surgery , Treatment Outcome , Surgical Flaps , Plastic Surgery Procedures , Skin Transplantation , Soft Tissue Injuries/surgery , Sutures , Perforator Flap
12.
Chinese Journal of Biotechnology ; (12): 4621-4634, 2023.
Article in Chinese | WPRIM (Western Pacific) | ID: wpr-1008046

ABSTRACT

Sialyllactose is one of the most abundant sialylated oligosaccharides in human milk oligosaccharides (HMOs), which plays an important role in the healthy development of infants and young children. However, its efficient and cheap production technology is still lacking presently. This study developed a two-step process employing multiple-strains for the production of sialyllactose. In the first step, two engineered strains, E. coli JM109(DE3)/ pET28a-BT0453 and JM109(DE3)/pET28a-nanA, were constructed to synthesize the intermediate N-acetylneuraminic acid. When the ratio of the biomass of the two engineered strains was 1:1 and the reaction time was 32 hours, the maximum yield of N-acetylneuraminic acid was 20.4 g/L. In the second step, E. coli JM109(DE3)/ pET28a-neuA, JM109(DE3)/ pET28a-nst and Baker's yeast were added to the above fermentation broth to synthesize 3'-sialyllactose (3'-SL). Using optimal conditions including 200 mmol/L N-acetyl-glucosamine and lactose, 150 g/L Baker's yeast, 20 mmol/L Mg2+, the maximum yield of 3'-SL in the fermentation broth reached 55.04 g/L after 24 hours of fermentation and the conversion rate of the substrate N-acetyl-glucosamine was 43.47%. This research provides an alternative technical route for economical production of 3'-SL.


Subject(s)
Child , Humans , Child, Preschool , N-Acetylneuraminic Acid , Escherichia coli/genetics , Lactose , Fermentation , Saccharomyces cerevisiae , Oligosaccharides , Glucosamine
13.
Article in Chinese | WPRIM (Western Pacific) | ID: wpr-1009035

ABSTRACT

OBJECTIVE@#To explore the effectiveness of hairpin shaped incision combined with cover-lifting flap in plastic surgery of huge fat pad on nape and back.@*METHODS@#Between March 2019 and March 2023, 10 patients with huge fat pad on the nape and back were treated. There was 1 male and 9 females with an average age of 52 years (range, 39-57 years). All patients had soft tissue bulge on the nape and back. Preoperative MRI showed the subcutaneous fat thickening. The length of the longitudinal axis of the fat pad ranged from 10.0 to 25.0 cm (mean, 14.1 cm), the length of the transverse axis ranged from 6.0 to 15.0 cm (mean, 10.8 cm); the thickness of the fat pad ranged from 2.5 to 5.1 cm (mean, 3.9 cm). Under general anesthesia, the patient was placed in a prone position and a hairpin shaped incision was made. The flap was lifted to remove the fat pad according to the marked area. The dressing was changed every 2 days after operation.@*RESULTS@#The operation time was 35-110 minutes (mean, 72 minutes). The intraoperative blood loss was 35-80 mL (mean, 49.5 mL). The drainage tube was removed at 2-5 days after operation (mean, 3.4 days). All incisions healed by first intention without incision dehiscence, infection, subcutaneous bruising, hematoma, or other related complications. All patients were followed up 2-24 months (mean, 12 months). All patients had a good shape of the nape and back and no noticeable scar on the incision. According to the Vancouver Scar Scale evaluation criteria, the incision scar score was 3-5 (mean, 3.7) at 2 months after operation. Patients had good neck movement with no recurrence.@*CONCLUSION@#For the huge fat pad on the nape and back, the plastic surgery using hairpin shaped incision and cover-lifting flap has the advantages of fully exposing the fat pad, concealed incision, simple operation, and natural shape of the nape and back after operation.


Subject(s)
Female , Humans , Male , Middle Aged , Surgery, Plastic , Cicatrix , Lifting , Plastic Surgery Procedures , Surgical Wound , Adipose Tissue
14.
Nanomicro Lett ; 14(1): 219, 2022 Nov 10.
Article in English | MEDLINE | ID: mdl-36355311

ABSTRACT

Metallic interface engineering is a promising strategy to stabilize Zn anode via promoting Zn2+ uniform deposition. However, strong interactions between the coating and Zn2+ and sluggish transport of Zn2+ lead to high anodic polarization. Here, we present a bio-inspired silk fibroin (SF) coating with amphoteric charges to construct an interface reversible electric field, which manipulates the transfer kinetics of Zn2+ and reduces anodic polarization. The alternating positively and negatively charged surface as a build-in driving force can expedite and homogenize Zn2+ flux via the interplay between the charged coating and adsorbed ions, endowing the Zn-SF anode with low polarization voltage and stable plating/stripping. Experimental analyses with theoretical calculations suggest that SF can facilitate the desolvation of [Zn(H2O)6]2+ and provide nucleation sites for uniform deposition. Consequently, the Zn-SF anode delivers a high-rate performance with low voltage polarization (83 mV at 20 mA cm-2) and excellent stability (1500 h at 1 mA cm-2; 500 h at 10 mA cm-2), realizing exceptional cumulative capacity of 2.5 Ah cm-2. The full cell coupled with ZnxV2O5·nH2O (ZnVO) cathode achieves specific energy of ~ 270.5/150.6 Wh kg-1 (at 0.5/10 A g-1) with ~ 99.8% Coulombic efficiency and retains ~ 80.3% (at 5.0 A g-1) after 3000 cycles.

15.
Nanomicro Lett ; 14(1): 128, 2022 Jun 14.
Article in English | MEDLINE | ID: mdl-35699828

ABSTRACT

Metallic zinc (Zn) is one of the most attractive multivalent-metal anode materials in post-lithium batteries because of its high abundance, low cost and high theoretical capacity. However, it usually suffers from large voltage polarization, low Coulombic efficiency and high propensity for dendritic failure during Zn stripping/plating, hindering the practical application in aqueous rechargeable zinc-metal batteries (AR-ZMBs). Here we demonstrate that anionic surfactant-assisted in situ surface alloying of Cu and Zn remarkably improves Zn reversibility of 3D nanoporous Zn electrodes for potential use as high-performance AR-ZMB anode materials. As a result of the zincophilic ZnxCuy alloy shell guiding uniform Zn deposition with a zero nucleation overpotential and facilitating Zn stripping via the ZnxCuy/Zn galvanic couples, the self-supported nanoporous ZnxCuy/Zn electrodes exhibit superior dendrite-free Zn stripping/plating behaviors in ambient aqueous electrolyte, with ultralow polarizations under current densities up to 50 mA cm‒2, exceptional stability for 1900 h and high Zn utilization. This enables AR-ZMB full cells constructed with nanoporous ZnxCuy/Zn anode and KzMnO2 cathode to achieve specific energy of as high as ~ 430 Wh kg‒1 with ~ 99.8% Coulombic efficiency, and retain ~ 86% after long-term cycles for > 700 h.

16.
Nat Commun ; 13(1): 576, 2022 Jan 31.
Article in English | MEDLINE | ID: mdl-35102182

ABSTRACT

Aqueous aluminum batteries are promising post-lithium battery technologies for large-scale energy storage applications because of the raw materials abundance, low costs, safety and high theoretical capacity. However, their development is hindered by the unsatisfactory electrochemical behaviour of the Al metal electrode due to the presence of an oxide layer and hydrogen side reaction. To circumvent these issues, we report aluminum-copper alloy lamellar heterostructures as anode active materials. These alloys improve the Al-ion electrochemical reversibility (e.g., achieving dendrite-free Al deposition during stripping/plating cycles) by using periodic galvanic couplings of alternating anodic α-aluminum and cathodic intermetallic Al2Cu nanometric lamellas. In symmetric cell configuration with a low oxygen concentration (i.e., 0.13 mg L-1) aqueous electrolyte solution, the lamella-nanostructured eutectic Al82Cu18 alloy electrode allows Al stripping/plating for 2000 h with an overpotential lower than ±53 mV. When the Al82Cu18 anode is tested in combination with an AlxMnO2 cathode material, the aqueous full cell delivers specific energy of ~670 Wh kg-1 at 100 mA g-1 and an initial discharge capacity of ~400 mAh g-1 at 500 mA g-1 with a capacity retention of 83% after 400 cycles.

17.
Article in English | WPRIM (Western Pacific) | ID: wpr-979983

ABSTRACT

@#Introduction: Sarcopenia is one of the geriatric syndromes affecting the ability of older adults to lead an independent living. However, its risk factors among Malaysian older adults are yet to be determined. This study investigated the prevalence and risk factors of sarcopenia among community-dwelling older adults in Klang Valley. Methods: This cross-sectional study involved 393 Malaysians aged 60 and above, residing in urban areas of Klang Valley recruited through convenience sampling. Socio-demographic and food intake information were obtained using validated questionnaires. Cut-off points for sarcopenia screening were obtained from the Asian Working Group of Sarcopenia(AWGS) while body impedance analysis(BIA) was employed to determine skeletal muscle index. A handgrip dynamometer was used to assess dominant handgrip strength and a 6-meter gait speed test was used to determine walking speed. Binary logistic regression analysis was used to determine the risk factors of sarcopenia. Results: Prevalence of sarcopenia was 33.6% and women(35.9%) were more affected compared to men(30.1%). The mean age of women assessed to have sarcopenia(69.1±6.5 years old) was higher compared to men(68.3±5.8 years old) (p<0.05). After adjusting for confounding factors, older adults with one year increased in age and one mg decreased in habitual dietary iron intake were estimated to be 1.08 times and 0.93 times the chances to have sarcopenia respectively. Conclusion: Approximately one-third of community-dwelling older adults in Klang Valley were assessed to have sarcopenia. Older adults aged 60 years and above and those with low dietary iron intake were at an increased risk of developing sarcopenia.

18.
ChemSusChem ; 14(20): 4593-4600, 2021 Oct 20.
Article in English | MEDLINE | ID: mdl-34418314

ABSTRACT

Nitrogen fixation to produce ammonia is a vital process since nitrogen is an essential element for the human body. Industrial nitrogen fixation mainly relies on the Haber-Bosch process. However, this process requires huge energy consumption and leads to pollution emission. In this study, the behaviors of intermediates in the nitrogen reduction reaction (NRR) are investigated for fifteen double-atom catalysts (DACs) through density functional theory calculations, revealing that under the synergistic effect of active sites on appropriate DACs, intermediates can be adsorbed through different configurations according to the activity improvement needs. VFe-N-C shows the best catalytic activity for electrochemical NRR with a limiting potential of -0.36 V vs. the reversible hydrogen electrode. The proposed synergistic effect of active sites on DACs for NRR could provide a new method for design of NRR catalysts.


Subject(s)
Ammonia/chemistry , Nitrogen Fixation , Nitrogen/chemistry , Adsorption , Catalysis , Catalytic Domain , Density Functional Theory , Electrochemical Techniques , Electrodes , Graphite/chemistry , Hydrogen/chemistry , Molecular Conformation , Oxidation-Reduction , Surface Properties
19.
Small ; 17(35): e2100683, 2021 Sep.
Article in English | MEDLINE | ID: mdl-34310042

ABSTRACT

Designing highly selective and cost-effective electrocatalysts toward electrochemical carbon dioxide (CO2 ) reduction is crucial for desirable transformation of greenhouse gas into fuels or high-value chemical products. Here, the authors report intermetallic Cu3 Sn that is in situ formed and seamlessly integrated on self-supported bimodal nanoporous Cu skeleton (Cu3 Sn/Cu) via a spontaneous alloying of Sn and Cu as robust electrocatalyst for selective electroreduction of CO2 to CO. By virtue of Sn atoms strengthening CO adsorption on Cu atoms, the intermetallic Cu3 Sn has an intrinsic activity of ≈10.58 µA cm-2 , more than 80-fold higher than that of monometallic Cu. By virtue of hierarchical bicontinuous nanoporous Cu architecture facilitating electron transfer and CO2 and proton mass transport and offering high specific surface areas for full use of electroactive Cu3 Sn sites, the nanoporous Cu3 Sn/Cu hybrid electrodes produce CO at a low overpotential of 0.09 V, and exhibit high partial current density of ≈15 mA cm-2 geo at overpotential of 0.59 V, along with excellent stability and selectivity of 91.5% Faradaic efficiency. The outstanding electrochemical performance make them attractive alternatives to precious Au- and Ag-based electrocatalysts for building low-cost CO2 electrolyzers to selectively produce CO.

20.
ChemSusChem ; 14(10): 2255-2261, 2021 May 20.
Article in English | MEDLINE | ID: mdl-33851508

ABSTRACT

CO methanation from electrochemical CO reduction reaction (CORR) is significant for sustainable environment and energy, but electrocatalysts with excellent selectivity and activity are still lacking. Selectivity is sensitive to the structure of active sites, and activity can be tailored by work function. Moreover, intrinsic active sites usually possess relatively high concentration compared to artificial ones. Here, antisite defects MoS2 and WS2 , intrinsic atomic defects of MoS2 and WS2 with a transition metal atom substituting a S2 column, were investigated for CORR by density functional theory calculations. The steric hindrance from the special bowl structure of MoS2 and WS2 ensured good selectivity towards CO methanation. Coordination environment variation of the active sites, the under-coordinated Mo or W atoms, effectively lowered the work function, making MoS2 and WS2 highly active for CO methanation with the required potential of -0.47 and -0.49 V vs. reversible hydrogen electrode, respectively. Moreover, high concentration of active sites and minimal structural deformation during the catalytic process of MoS2 and WS2 enhanced their attraction for future commercial application.

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