Staff directory Xiang Zhang

Xiang Zhang

Fellowship Doctoral Student
China Scholarship Council (CSC),
Universidad Autónoma de Barcelona (UAB)
xiang.zhang(ELIMINAR)@icn2.cat
Supramolecular NanoChemistry and Materials

Publications

2022

  • Critical Role of Phosphorus in Hollow Structures Cobalt-Based Phosphides as Bifunctional Catalysts for Water Splitting

    Zhang W., Han N., Luo J., Han X., Feng S., Guo W., Xie S., Zhou Z., Subramanian P., Wan K., Arbiol J., Zhang C., Liu S., Xu M., Zhang X., Fransaer J. Small; 18 (4, 2103561) 2022. 10.1002/smll.202103561. IF: 13.281

    Cobalt phosphides electrocatalysts have great potential for water splitting, but the unclear active sides hinder the further development of cobalt phosphides. Wherein, three different cobalt phosphides with the same hollow structure morphology (CoP-HS, CoP2-HS, CoP3-HS) based on the same sacrificial template of ZIF-67 are prepared. Surprisingly, these cobalt phosphides exhibit similar OER performances but quite different HER performances. The identical OER performance of these CoPx-HS in alkaline solution is attributed to the similar surface reconstruction to CoOOH. CoP-HS exhibits the best catalytic activity for HER among these CoPx-HS in both acidic and alkaline media, originating from the adjusted electronic density of phosphorus to affect absorption–desorption process on H. Moreover, the calculated ΔGH* based on P-sites of CoP-HS follows a quite similar trend with the normalized overpotential and Tafel slope, indicating the important role of P-sites for the HER process. Moreover, CoP-HS displays good performance (cell voltage of 1.67 V at a current density of 50 mA cm−2) and high stability in 1 M KOH. For the first time, this work detailly presents the critical role of phosphorus in cobalt-based phosphides for water splitting, which provides the guidance for future investigations on transition metal phosphides from material design to mechanism understanding. © 2021 Wiley-VCH GmbH


  • Engineering the Interfacial Microenvironment via Surface Hydroxylation to Realize the Global Optimization of Electrochemical CO2Reduction

    Han X., Zhang T., Biset-Peiró M., Zhang X., Li J., Tang W., Tang P., Morante J.R., Arbiol J. ACS Applied Materials and Interfaces; 14 (28): 32157 - 32165. 2022. 10.1021/acsami.2c09129.

    The adsorption and activation of CO2 on the electrode interface is a prerequisite and key step for electrocatalytic CO2 reduction reaction (eCO2 RR). Regulating the interfacial microenvironment to promote the adsorption and activation of CO2 is thus of great significance to optimize overall conversion efficiency. Herein, a CO2-philic hydroxyl coordinated ZnO (ZnO-OH) catalyst is fabricated, for the first time, via a facile MOF-assisted method. In comparison to the commercial ZnO, the as-prepared ZnO-OH exhibits much higher selectivity toward CO at lower applied potential, reaching a Faradaic efficiency of 85% at -0.95 V versus RHE. To the best of our knowledge, such selectivity is one of the best records in ZnO-based catalysts reported till date. Density functional theory calculations reveal that the coordinated surficial -OH groups are not only favorable to interact with CO2 molecules but also function in synergy to decrease the energy barrier of the rate-determining step and maintain a higher charge density of potential active sites as well as inhibit undesired hydrogen evolution reaction. Our results indicate that engineering the interfacial microenvironment through the introduction of CO2-philic groups is a promising way to achieve the global optimization of eCO2 RR via promoting adsorption and activation of CO2. © 2022 The Authors. Published by American Chemical Society.


  • Site-Specific Axial Oxygen Coordinated FeN4 Active Sites for Highly Selective Electroreduction of Carbon Dioxide

    Zhang T., Han X., Liu H., Biset-Peiró M., Li J., Zhang X., Tang P., Yang B., Zheng L., Morante J.R., Arbiol J. Advanced Functional Materials; 32 (18, 2111446) 2022. 10.1002/adfm.202111446. IF: 18.808

    Regulating the coordination environment via heteroatoms to break the symmetrical electronic structure of M-N4 active sites provides a promising route to engineer metal-nitrogen-carbon catalysts for electrochemical CO2 reduction reaction. However, it remains challenging to realize a site-specific introduction of heteroatoms at atomic level due to their energetically unstable nature. Here, this paper reports a facile route via using an oxygen- and nitrogen-rich metal–organic framework (MOF) (IRMOF-3) as the precursor to construct the Fe-O and Fe-N chelation, simultaneously, resulting in an atomically dispersed axial O-coordinated FeN4 active site. Compared to the FeN4 active sites without O coordination, the formed FeN4-O sites exhibit much better catalytic performance toward CO, reaching a maximum FECO of 95% at −0.50 V versus reversible hydrogen electrode. To the best of the authors’ knowledge, such performance exceeds that of the existing Fe-N-C-based catalysts derived from sole N-rich MOFs. Density functional theory calculations indicate that the axial O-coordination regulates the binding energy of intermediates in the reaction pathways, resulting in a smoother desorption of CO and increased energy for the competitive hydrogen production. © 2022 Wiley-VCH GmbH.


2021

  • Control of spin-charge conversion in van der Waals heterostructures

    Galceran R., Tian B., Li J., Bonell F., Jamet M., Vergnaud C., Marty A., García J.H., Sierra J.F., Costache M.V., Roche S., Valenzuela S.O., Manchon A., Zhang X., Schwingenschlögl U. APL Materials; 9 (10, 100901) 2021. 10.1063/5.0054865. IF: 5.096

    The interconversion between spin and charge degrees of freedom offers incredible potential for spintronic devices, opening routes for spin injection, detection, and manipulation alternative to the use of ferromagnets. The understanding and control of such interconversion mechanisms, which rely on spin-orbit coupling, is therefore an exciting prospect. The emergence of van der Waals materials possessing large spin-orbit coupling (such as transition metal dichalcogenides or topological insulators) and/or recently discovered van der Waals layered ferromagnets further extends the possibility of spin-to-charge interconversion to ultrathin spintronic devices. Additionally, they offer abundant room for progress in discovering and analyzing novel spin-charge interconversion phenomena. Modifying the properties of van der Waals materials through proximity effects is an added degree of tunability also under exploration. This Perspective discusses the recent advances toward spin-to-charge interconversion in van der Waals materials. It highlights scientific developments which include techniques for large-scale growth, device physics, and theoretical aspects. © 2021 Author(s).


  • Ferromagnetic metallic Sr-rich Ln1/2A1/2CoO3 cobaltites with spontaneous spin rotation

    Padilla-Pantoja J., Romaguera A., Zhang X., Herrero-Martín J., Fauth F., Blasco J., García-Muñoz J.L. Physical Review B; 104 (5, 054411) 2021. 10.1103/PhysRevB.104.054411. IF: 4.036

    The Pr0.50Sr0.50CoO3 perovskite exhibits unique magnetostructural properties among the rest of ferromagnetic (FM)/metallic Ln0.50Sr0.50CoO3 compounds. The sudden orthorhombic-tetragonal (Imma→I4/mcm) structural transition produces an unusual magnetic behavior vs temperature and external magnetic fields. The symmetry change is responsible for a spontaneous spin rotation in this metallic oxide. We have studied half-doped Ln0.50(Sr1-xAx)0.50CoO3 cobaltites varying the ionic radius rA of A-site cations (divalent cations and lanthanides) to complete the T-rA phase diagram. The influence of the structural distortion and the A-cation size for the occurrence of a spontaneous spin reorientation in the metallic state has been investigated. As the magnetization reorientation is driven by the temperature-induced collapse of the orthorhombic distortion, a careful investigation of the structural symmetry is presented, varying the structural distortion of the Sr-rich half-doped cobaltites by means of both compositional and temperature changes. The region in the phase diagram of these FM/metallic cobaltites where Fm′m′m magnetic symmetry replaces Im′m′a was determined. In that region, the magnetization direction has rotated 45 ° within the a-b plane from the former to the latter. © 2021 American Physical Society.


  • Mesoporous silica coated CeO2nanozymes with combined lipid-lowering and antioxidant activity induce long-term improvement of the metabolic profile in obese Zucker rats

    Parra-Robert M., Zeng M., Shu Y., Fernández-Varo G., Perramón M., Desai D., Chen J., Guo D., Zhang X., Morales-Ruiz M., Rosenholm J.M., Jiménez W., Puntes V., Casals E., Casals G. Nanoscale; 13 (18): 8452 - 8466. 2021. 10.1039/d1nr00790d. IF: 7.790

    Obesity is one of the most important public health problems that is associated with an array of metabolic disorders linked to cardiovascular disease, stroke, type 2 diabetes, and cancer. A sustained therapeutic approach to stop the escalating prevalence of obesity and its associated metabolic comorbidities remains elusive. Herein, we developed a novel nanocomposite based on mesoporous silica coated cerium oxide (CeO2) nanozymes that reduce the circulating levels of fatty acids and remarkably improve the metabolic phenotype in a model of obese Zucker rats five weeks after its administration. Lipidomic and gene expression analyses showed an amelioration of the hyperlipidemia and of the hepatic and adipose metabolic dysregulations, which was associated with a down-regulation of the hepatic PI3K/mTOR/AKT pathway and a reduction of the M1 proinflammatory cytokine TNF-a. In addition, the coating of the CeO2 maximized its cell antioxidant protective effects and minimized non-hepatic biodistribution. The one-pot synthesis method for the nanocomposite fabrication is implemented entirely in aqueous solution, room temperature and open atmosphere conditions, favoring scalability and offering a safe and translatable lipid-lowering and antioxidant nanomedicine to treat metabolic comorbidities associated with obesity. This approach may be further applied to address other metabolic disorders related to hyperlipidemia, low-grade inflammation and oxidative stress. © 2021 The Royal Society of Chemistry.


  • Quasi-double-star nickel and iron active sites for high-efficiency carbon dioxide electroreduction

    Zhang T., Han X., Liu H., Biset-Peiró M., Zhang X., Tan P., Tang P., Yang B., Zheng L., Morante J.R., Arbiol J. Energy and Environmental Science; 14 (9): 4847 - 4857. 2021. 10.1039/d1ee01592c. IF: 38.532

    Although the Faraday efficiencies (FEs) obtained on most of the Ni based single-atom catalysts (Ni-N-C) are satisfactory (generally >90%) for the electrochemical transfer CO2 to CO, their practical application is still limited by their high overpotentials (>600 mV vs. RHE), which implies a higher energy consumption to drive the CO2 RR. In this work, we have prepared a quasi-double star catalyst composed of nearby Ni and Fe active sites via a simple pyrolysis of Ni and Fe co-doped Zn-based MOFs in order to achieve a high selectivity at a low overpotential during the CO2 RR. Specifically, the optimized Ni/Fe-N-C catalyst shows an exclusive selectivity (a maximum FE(CO) of 98%) at a low overpotential of 390 mV vs. RHE, which is superior to both the single metal counterparts (Ni-N-C and Fe-N-C catalysts) and other state-of-the-art M-N-C catalysts. The DFT results further reveal that regulating the catalytic CO2 RR performance via nearby Ni and Fe active sites can potentially break the activity benchmark of the single metal counterparts because the neighboring Ni and Fe active sites not only function in synergy to decrease the reaction barrier for the formation of COOH∗ and desorption of CO∗ in comparison to their single metal counterparts, but also prevent the undesired hydrogen evolution reaction (HER). This work presents a quasi-double-star catalyst composed of two metal sites for high-efficiency CO2 reduction, which paves the way for the rational design of bimetallic catalysts with separated active sites for other reactions. © The Royal Society of Chemistry.


2019

  • From rational design of a new bimetallic MOF family with tunable linkers to OER catalysts

    Zhang X., Luo J., Wan K., Plessers D., Sels B., Song J., Chen L., Zhang T., Tang P., Morante J.R., Arbiol J., Fransaer J. Journal of Materials Chemistry A; 7 (4): 1616 - 1628. 2019. 10.1039/c8ta08508k. IF: 10.733

    Innovative bimetallic MOFs offer more possibilities to further tailor the properties of MOFs, which have attracted great attention for wide applications. However, it is still a great challenge to rationally design bimetallic MOFs due to the lack of a tunable and reasonable hybrid structure architecture. Herein, a new series of bimetallic metal-organic frameworks (MOFs) with tunable pillar linkers were prepared by a one-step synthesis method. These bimetallic MOFs retain the same crystal structure when the mole fraction (based on metal) of the two metals changes from 0 to 1 and both metal ions occupy random nodal positions. The incorporation of a second metal cation has a large influence on the intrinsic properties (e.g. thermal stabilities and band gaps) of the MOFs. Furthermore, these bimetallic MOFs were used as self-sacrificial templates to prepare bimetal oxide catalysts for the oxygen evolution reaction (OER). After pyrolysis, a porous and hierarchical honeycomb-like structure with carbon network covered (bi)metal oxides is formed. Among all the bimetallic MOF-derived catalysts, CoNi1@C showed the best performance for the OER with the lowest Tafel slopes (55.6 mV dec -1 ) and overpotentials (335 mV on a glassy carbon electrode and 276 mV on Ni foam) at a current density of 10 mA cm -2 , which is higher than those of state-of-the-art Co-Ni mixed oxide catalysts derived from MOFs for the OER. Our results indicate that the incorporation of a second metal ion is a promising strategy to tailor the properties of MOFs. More importantly, this new bimetallic MOF family with tunable linkers is expected to serve as a flexible assembly platform to offer broad possibilities for practical applications of MOFs. © 2019 The Royal Society of Chemistry.


  • Hierarchical Porous Ni 3 S 4 with Enriched High-Valence Ni Sites as a Robust Electrocatalyst for Efficient Oxygen Evolution Reaction

    Wan K., Luo J., Zhou C., Zhang T., Arbiol J., Lu X., Mao B.-W., Zhang X., Fransaer J. Advanced Functional Materials; 29 (18, 1900315) 2019. 10.1002/adfm.201900315. IF: 15.621

    Electrochemical water splitting is a common way to produce hydrogen gas, but the sluggish kinetics of the oxygen evolution reaction (OER) significantly limits the overall energy conversion efficiency of water splitting. In this work, a highly active and stable, meso–macro hierarchical porous Ni 3 S 4 architecture, enriched in Ni 3+ is designed as an advanced electrocatalyst for OER. The obtained Ni 3 S 4 architectures exhibit a relatively low overpotential of 257 mV at 10 mA cm −2 and 300 mV at 50 mA cm −2 . Additionally, this Ni 3 S 4 catalyst has excellent long-term stability (no degradation after 300 h at 50 mA cm −2 ). The outstanding OER performance is due to the high concentration of Ni 3+ and the meso–macro hierarchical porous structure. The presence of Ni 3+ enhances the chemisorption of OH − , which facilitates electron transfer to the surface during OER. The hierarchical porosity increases the number of exposed active sites, and facilitates mass transport. A water-splitting electrolyzer using the prepared Ni 3 S 4 as the anode catalyst and Pt/C as the cathode catalyst achieves a low cell voltage of 1.51 V at 10 mA cm −2 . Therefore, this work provides a new strategy for the rational design of highly active OER electrocatalysts with high valence Ni 3+ and hierarchical porous architectures. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim


  • Tailor-made metal-nitrogen-carbon bifunctional electrocatalysts for rechargeable Zn-air batteries via controllable MOF units

    Zhang X., Luo J., Lin H.-F., Tang P., Morante J.R., Arbiol J., Wan K., Mao B.-W., Liu L.-M., Fransaer J. Energy Storage Materials; 17: 46 - 61. 2019. 10.1016/j.ensm.2018.11.034. IF: 0.000

    The majority of chemical syntheses involve the use of catalysts, which play a crucial role in the yield and conversion rates of chemical reactions. In view of the increasing demand for chemical commodities and specialties linked to the growth of the world's population and the living standards, highly efficient and low-cost catalysts are urgently required. The metal-nitrogen-carbon (M-N-C) catalysts family is one of the most promising candidates. In this work, a series of benzene-1,3,5-tricarboxylate linker based metal organic frameworks (MOFs) were used as self-sacrificial templates and tunable platform for designable preparation of M-N-C catalysts. Changing the pillars between the 2D layers and the nature of the metal ions in the pristine MOFs significantly influenced the structure, chemical composition and catalytic activity of the resulting M-N-C catalysts for the oxygen reduction reaction (ORR). Furthermore, the influence of the MOF units on the catalyst performance, the role of the metals in the M-N-C catalysts and the primary catalytically active sites for ORR were explored by a combination of density functional theory (DFT), in-depth structural and chemical/elemental characterizations, and electrochemical studies. Among the prepared catalysts, Co-BTC-bipy-700 exhibited the highest electrocatalytic activity for oxygen reduction reaction (ORR), which showed a larger limiting current density and similar half-wave potentials with less catalyst degradation and much higher methanol tolerance than the commercial Pt/C catalyst. Meanwhile, as a bifunctional electrocatalyst, Co-BTC-bipy-700 catalyst was also employed for oxygen evolution reaction (OER) and demonstrated a lower overpotential (lowered by 140 mV at a current density of 10 mA cm−2) and better durability than IrO2. Furthermore, in terms of device performance, the Zn-air battery enabled by Co-BTC-bipy-700 catalyst reached a maximum specific energy as high as 1009.8 Wh kg−1, which is 76.5% of the theoretical value (1320 Wh kg−1), and demonstrated higher discharge potential and lower charge potential than that based on the Pt/C catalyst. Importantly, the presented strategy for tailor-made M-N-C catalysts by controlling the synthesis of the pristine MOFs could offer a guide map for the future design of M-N-C catalysts family not only for electrochemical reactions but also beyond electrochemistry. © 2018 Elsevier B.V.


2018

  • Ultrasensitive binder-free glucose sensors based on the pyrolysis of in situ grown Cu MOF

    Zhang X., Luo J., Tang P., Morante J.R., Arbiol J., Xu C., Li Q., Fransaer J. Sensors and Actuators, B: Chemical; 254: 272 - 281. 2018. 10.1016/j.snb.2017.07.024. IF: 5.667

    A non-enzymatic glucose sensor based on carbon/Cu composite materials was developed by the in-situ growth and subsequent pyrolysis of metal-organic frameworks (MOFs) on Cu foam. After pyrolysis, SEM, HRTEM and STEM-EELS were employed to clarify the hierarchical Cu@porous carbon electrode. It is found that the Cu nanoparticles are uniformly embedded in the carbon matrix, carbon matrix in close contact with the pyrolized carbon sheets. The electrocatalytic activity of the Cu@porous carbon matrix electrode for glucose sensing was explored by cyclic voltammetry (CV) and chronoamperometry. The resulting Cu@porous carbon matrix electrode displays ultrahigh sensitivity (10.1 mA cm−2 mM−1), low detection limit (0.6 μM), short response time (less than 2 s) and good stability, indicating that the developed electrode is a promising glucose sensor. © 2017 Elsevier B.V.


2017

  • A universal strategy for metal oxide anchored and binder-free carbon matrix electrode: A supercapacitor case with superior rate performance and high mass loading

    Zhang X., Luo J., Tang P., Ye X., Peng X., Tang H., Sun S.-G., Fransaer J. Nano Energy; 31: 311 - 321. 2017. 10.1016/j.nanoen.2016.11.024. IF: 12.343

    Despite the significant advances in preparing carbon-metal oxide composite electrodes, strategies for seamless interconnecting of these two materials without using binders are still scarce. Herein we design a novel method for in situ synthesis of porous 2D-layered carbon–metal oxide composite electrode. Firstly, 2D-layered Ni-Co mixed metal-organic frameworks (MOFs) are deposited directly on nickel foam by anodic electrodeposition. Subsequent pyrolysis and activation procedure lead to the formation of carbon–metal oxides composite electrodes. Even with an ultrahigh mass loading of 13.4 mg cm−2, the as-prepared electrodes exhibit a superior rate performance of 93% (from 1 to 20 mA cm−2), high capacitance (2098 mF cm−2 at a current density of 1 mA cm−2), low resistance and excellent cycling stability, making them promising candidates for practical supercapacitor application. As a proof of concept, several MOF derived electrodes with different metal sources have also been prepared successfully via the same route, demonstrating the versatility of the proposed method for the preparation of binder-free carbon–metal oxide composite electrodes for electrochemical devices. © 2016 Elsevier Ltd


2016

  • Synergistic effects in 3D honeycomb-like hematite nanoflakes/branched polypyrrole nanoleaves heterostructures as high-performance negative electrodes for asymmetric supercapacitors

    Tang P.-Y., Han L.-J., Genç A., He Y.-M., Zhang X., Zhang L., Galán-Mascarós J.R., Morante J.R., Arbiol J. Nano Energy; 22: 189 - 201. 2016. 10.1016/j.nanoen.2016.02.019. IF: 11.553

    Rational assembly of unique branched heterostructures is one of the facile techniques to improve the electrochemical figure of merit of materials. By taking advantages of hydrogen bubbles dynamic template, hydrothermal method and electrochemical polymerization, branched polypyrrole (PPy) nanoleaves decorated honeycomb-like hematite nanoflakes (core-branch Fe2O3@PPy) are fabricated. X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy (TEM), high-resolution TEM, and scanning transmission electron microscopy in high angle annular dark field mode with electron energy loss spectroscopy were combined to elucidate the mechanisms underlying formation and morphogenesis evolution of core-branch Fe2O3@PPy heterostructures. Benefiting from the stability of honeycomb-like hematite nanoflakes and the high conductivity of PPy nanoleaves, the resultant core-branch Fe2O3@PPy exhibits an ultrahigh capacitance of 1167.8 F g-1 at 1 A g-1 in 0.5 M Na2SO4 aqueous solution. Moreover, the assembled bi-metal oxides asymmetric supercapacitor (Fe2O3@PPy//MnO2) gives rise to a maximum energy density of 42.4 W h kg-1 and a maximum power density of 19.14 kW kg-1 with an excellent cycling performance of 97.1% retention after 3000 cycles at 3 A g-1. These performance features are superior than previous reported iron oxide/hydroxides based supercapacitors, offering an important guideline for future design of advanced next-generation supercapacitors. © 2016 Elsevier Ltd.