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1.
Developing efficient, durable, and earth‐abundant electrocatalysts for both hydrogen and oxygen evolution reactions is important for realizing large‐scale water splitting. The authors report that FeB2 nanoparticles, prepared by a facile chemical reduction of Fe2+ using LiBH4 in an organic solvent, are a superb bifunctional electrocatalyst for overall water splitting. The FeB2 electrode delivers a current density of 10 mA cm?2 at overpotentials of 61 mV for hydrogen evolution reaction (HER) and 296 mV for oxygen evolution reaction (OER) in alkaline electrolyte with Tafel slopes of 87.5 and 52.4 mV dec?1, respectively. The electrode can sustain the HER at an overpotential of 100 mV for 24 h and OER for 1000 cyclic voltammetry cycles with negligible degradation. Density function theory calculations demonstrate that the boron‐rich surface possesses appropriate binding energy for chemisorption and desorption of hydrogen‐containing intermediates, thus favoring the HER process. The excellent OER activity of FeB2 is ascribed to the formation of a FeOOH/FeB2 heterojunction during water oxidation. An alkaline electrolyzer is constructed using two identical FeB2‐NF electrodes as both anode and cathode, which can achieve a current density of 10 mA cm?2 at 1.57 V for overall water splitting with a faradaic efficiency of nearly 100%, rivalling the integrated state‐of‐the‐art Pt/C and RuO2/C.  相似文献   

2.
The development of highly efficient and low‐cost electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is paramount for water splitting associated with the storage of clean and renewable energy. Here, this study reports its findings in the development of a nanostructured perovskite oxide as OER/HER bifunctional electrocatalyst for overall water splitting. Prepared by a facile electrospinning method, SrNb0.1Co0.7Fe0.2O3–δ perovskite nanorods (SNCF‐NRs) display excellent OER and HER activity and stability in an alkaline solution, benefiting from the catalytic nature of perovskites and unique structural features. More importantly, the SNCF‐NR delivers a current density of 10 mA cm?2 at a cell voltage of merely ≈1.68 V while maintaining remarkable durability when used as both anodic and cathodic catalysts in an alkaline water electrolyzer. The performance of this bifunctional perovskite material is among the best ever reported for overall water splitting, offering a cost‐effective alternative to noble metal based electrocatalysts.  相似文献   

3.
The controllable synthesis of single‐crystallized iron‐cobalt carbonate hydroxide nanosheets array on 3D conductive Ni foam (FCCH/NF) as a monolithic oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) bifunctional electrocatalyst for full water splitting is described. The results demonstrate that the incorporation of Fe can effectively tune the morphology, composition, electronic structure, and electrochemical active surface area of the electrocatalysts, thus greatly enhancing the intrinsic electrocatalytic activity. The optimal electrocatalyst (F0.25C1CH/NF) can deliver 10 and 1000 mA cm?2 at very small overpotentials of 77 and 256 mV for HER and 228 and 308 mV for OER in 1.0 m KOH without significant interference from gas evolution. The F0.25C1CH‐based two‐electrode alkaline water electrolyzer only requires cell voltages of 1.45 and 1.52 V to achieve current densities of 10 and 500 mA cm?2. The results demonstrate that such fascinating electrocatalytic activity can be ascribed to the increase in the catalytic active surface area, facilitated electron and mass transport properties, and the synergistic interactions because of the incorporation of Fe.  相似文献   

4.
The development of highly active and robust non-noble-metal electrocatalysts for alkaline hydrogen evolution reaction (HER) at industrial-level current density is the key for industrialization of alkaline water electrolysis. Herein, a superhydrophilic self-supported Ni/Y2O3 heterostructural electrocatalyst is constructed by a high-temperature selective reduction method, which demonstrates excellent catalytic performance for alkaline HER at high current density. Concretely, this catalyst can drive 10 mA cm−2 at a low overpotential of 61.1 ± 3.7 mV, with a low Tafel slope of 52.8 mV dec−1. Moreover, it also shows outstanding long-term durability at high current density of 1000 mA cm−2 for 500 h in 1 m  KOH, evidently exceeding the metallic Ni and Pt/C(20%) catalysts. The superior HER activity can be attributed to the multi-interface engineering of the Ni/Y2O3 electrode. Construction of Ni/Y2O3 heterogeneous interface with dual active sites lowers the energy barrier of water dissociation and optimizes the hydrogen adsorption energy, thus synergistically accelerating the overall HER kinetics. Also, its superhydrophilic self-supported electrode structure with the firm electrocatalyst-substrate interface and weakened electrocatalyst-bubble interfacial force ensures rapid charge transfer, prevents catalyst shedding, and expedites the H2 gas bubble release timely, further enhancing the catalytic activity and stability at high current density.  相似文献   

5.
The development of Pt‐free catalysts for the alkaline hydrogen evolution reaction (HER), which is widely used in industrial scale water‐alkali electrolyzers, remains a contemporary and pressing challenge. Ruthenium (Ru) has excellent water‐dissociation abilities and could be an alternative water splitting catalyst. However, its large hydrogen binding energy limits HER activity. Here, a new approach is proposed to boost the HER activity of Ru through uniform loading of Ru nanoparticles on triazine‐ring (C3N3)‐doped carbon (triNC). The composite (Ru/triNC) exhibits outstanding HER activity with an ultralow overpotential of ≈2 mV at 10 mA cm?2; thereby making it the best performing electrocatalyst hitherto reported for alkaline HER. The calculated metal mass activity of Ru/triNC is >10 and 15 times higher than that of Pt/C and Pt/triNC. Both theoretical and experimental studies reveal that the triazine‐ring is a good match for Ru to weaken the hydrogen binding on Ru through interfacial charge transfer via increased contact electrification. Therefore, Ru/triNC can provide the optimal hydrogen adsorption free energy (approaching zero), while maintaining the strong water‐dissociation activity. This study provides a new avenue for designing highly efficient and stable electrocatalysts for water splitting.  相似文献   

6.
Benefiting from ordered atomic structures and strong d-orbital interactions, intermetallic compounds (IMCs) are promising electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, the body-centered cubic IrGa IMCs with atomic donor–acceptor architectures are synthesized and anchored on the nitrogen-doped reduced graphene oxide (i.e., IrGa/N-rGO). Structural characterizations and theoretical calculations reveal that the electron-rich Ir sites are atomically dispersed in IrGa/N-rGO, facilitating the electron transfer between Ir atoms and adsorbed species, which can efficiently decrease the energy barriers of the potential determining step for both HER and OER. Impressively, the IrGa/N-rGO||IrGa/N-rGO exhibits excellent performance for overall water splitting in alkaline medium, requiring a low cell voltage of 1.51 V to achieve 10 mA cm−2, meanwhile, exhibiting no significant degradation for 100 h. This work demonstrates that the rational design of noble metal electrocatalysts with donor–acceptor architectures is beneficial for catalytic reactions in energy conversion applications.  相似文献   

7.
Water splitting is a promising technology for sustainable conversion of hydrogen energy. The rational design of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) bifunctional electrocatalysts with superior activity and stability in the same electrolyte is the key to promoting their large‐scale applications. Herein, an ultralow Ru (1.08 wt%) transition metal phosphide on nickel foam (Ru–MnFeP/NF) derived from Prussian blue analogue, that effectively drivies both the OER and the HER in 1 m KOH, is reported. To reach 20 mA cm?2 for OER and 10 mA cm?2 for HER, the Ru–MnFeP/NF electrode only requires overpotentials of 191 and 35 mV, respectively. Such high electrocatalytic activity exceeds most transition metal phosphides for the OER and the HER, and even reaches Pt‐like HER electrocatalytic levels. Accordingly, it significantly accelerates full water splitting at 10 mA cm?2 with 1.470 V, which outperforms that of the integrated RuO2 and Pt/C couple electrode (1.560 V). In addition, the extremely long operational stability (50 h) and the successful demonstration of a solar‐to‐hydrogen generation system through full water splitting provide more flexibility for large‐scale applications of Ru–MnFeP/NF catalysts.  相似文献   

8.
Searching for highly efficient and cost‐effective electrocatalysts toward the hydrogen evolution reaction (HER) in alkaline electrolyte is highly desirable for the development of alkaline water splitting, but still remains a significant challenge. Herein, the rational design of Cr‐doped Co4N nanorod arrays grown on carbon cloth (Cr–Co4N/CC) that can efficiently catalyze the HER in alkaline media is reported. It displays outstanding performance, with the exceptionally small overpotential of 21 mV to obtain the current density of 10 mA cm?2 and good stability in 1.0 m KOH, which is even better than the commercial Pt/C electrocatalyst, and much lower than most of the reported transition metal nitride‐based and other non‐noble metal‐based electrocatalysts toward the alkaline HER. Density functional theory (DFT) calculations and experimental results reveal that the Cr atoms not only act as oxophilic sites for boosting water adsorption and dissociation, but also modulate the electronic structure of Co4N to endow optimized hydrogen binding abilities on Co atoms, thereby leading to accelerating both the alkaline Volmer and Heyrovsky reaction kinetics. In addition, this strategy can be extended to other metals (such as Mo, Mn, and Fe) doped Co4N electrocatalysts, thus may open up a new avenue for the rational design of highly efficient transition metal nitride‐based HER catalysts and beyond.  相似文献   

9.
Renewable electricity powered water electrolysis is a promising solution for the conversion and storage of the intermittent renewable energy resources in the form of hydrogen. Herein, atomically thin FeCoNi ternary (oxy)hydroxide nanosheets (FeCoNi‐ATNs) are developed as efficient and robust bifunctional electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in 1 m KOH solution (pH = 14). The electrocatalyst shows remarkably high apparent catalytic performance (400 mA cm?2 at 350 mV for OER and 240 mV for HER) and mass activities at modest overpotentials (1931 A g?1 at 330 mV for OER; 1819 A g?1 at 200 mV for HER). Moreover, the OER and HER performance of FeCoNi–ATNs are fully reversible and electrochemically switchable, due to the interconversion attribute of two catalytic states for OER and HER. Using the dual functional properties of this catalyst, a fully reversible water electrolyzer cell is fabricated, exhibiting a robust reversibility between two half reactions in water electrolysis under a high current density (100 mA cm?1), which can effectively overcome the stability issues caused by electrode depolarization during frequent power interruptions, an inevitable phenomenon commonly brought about by the usage of intermittent renewable energy supplies.  相似文献   

10.
Construction of well‐defined metal–organic framework precursor is vital to derive highly efficient transition metal–carbon‐based electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting. Herein, a novel strategy involving an in situ transformation of ultrathin cobalt layered double hydroxide into 2D cobalt zeolitic imidazolate framework (ZIF‐67) nanosheets grafted with 3D ZIF‐67 polyhedra supported on the surface of carbon cloth (2D/3D ZIF‐67@CC) precursor is proposed. After a low‐temperature pyrolysis, this precursor can be further converted into hybrid composites composed of ultrafine cobalt nanoparticles embedded within 2D N‐doped carbon nanosheets and 3D N‐doped hollow carbon polyhedra (Co@N‐CS/N‐HCP@CC). Experimental and density functional theory calculations results indicate that such composites have the advantages of a large number of accessible active sites, accelerated charge/mass transfer ability, the synergistic effect of components as well as an optimal water adsorption energy change. As a result, the obtained Co@N‐CS/N‐HCP@CC catalyst requires overpotentials of only 66 and 248 mV to reach a current density of 10 mA cm?2 for HER and OER in 1.0 m KOH, respectively. Remarkably, it enables an alkali‐electrolyzer with a current density of 10 mA cm?2 at a low cell voltage of 1.545 V, superior to that of the IrO2@CC||Pt/C@CC couple (1.592 V).  相似文献   

11.
It is urgently required to develop highly efficient and stable bifunctional non‐noble metal electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) for water splitting. In this study, a facile electrospinning followed by a post‐carbonization treatment to synthesize nitrogen‐doped carbon nanofibers (NCNFs) integrated with Ni and Mo2C nanoparticles (Ni/Mo2C‐NCNFs) as water splitting electrocatalysts is developed. Owing to the strong hydrogen binding energy on Mo2C and high electrical conductivity of Ni, synergetic effect between Ni and Mo2C nanoparticles significantly promote both HER and OER activities. The optimized hybrid (Ni/Mo2C(1:2)‐NCNFs) delivers low overpotentials of 143 mV for HER and 288 mV for OER at a current density of 10 mA cm?2. An alkaline electrolyzer with Ni/Mo2C(1:2)‐NCNFs as catalysts for both anode and cathode exhibits a current density of 10 mA cm?2 at a voltage of 1.64 V, which is only 0.07 V larger than the benchmark of Pt/C‐RuO2 electrodes. In addition, an outstanding long‐term durability during 100 h testing without obvious degradation is achieved, which is superior to most of the noble‐metal‐free electrocatalysts reported to date. This work provides a simple and effective approach for the preparation of low‐cost and high‐performance bifunctional electrocatalysts for efficient overall water splitting.  相似文献   

12.
A homologous Ni–Co based nanowire system, consisting of both nickel cobalt oxide and nickel cobalt sulfide nanowires, is developed for efficient, complementary water splitting. The spinel‐type nickel cobalt oxide (NiCo2O4) nanowires are hydrothermally synthesized and can serve as an excellent oxygen evolution reaction catalyst. Subsequent sulfurization of the NiCo2O4 nanowires leads to the formation of pyrite‐type nickel cobalt sulfide (Ni0.33Co0.67S2) nanowires. Due to the 1D nanowire morphology and enhanced charge transport capability, the Ni0.33Co0.67S2 nanowires function as an efficient, stable, and robust nonnoble metal electrocatalyst for hydrogen evolution reaction (HER), substantially exceeding CoS2 or NiS2 nanostructures synthesized under similar methods. The Ni0.33Co0.67S2 nanowires exhibit low onset potential of ?65, ?39, and ?50 mV versus reversible hydrogen electrode, Tafel slopes of 44, 68, and 118 mV dec?1 at acidic, neutral, and basic conditions, respectively, and excellent stability, comparable to the best reported non‐noble metal‐based HER catalysts. Furthermore, the homologous Ni0.33Co0.67S2 nanowires and NiCo2O4 nanowires are assembled into an all‐nanowire based water splitting electrolyzer with a current density of 5 mA cm?2 at a voltage as 1.65 V, thus suggesting a unique homologous, earth abundant material system for water splitting.  相似文献   

13.
Hydrogen evolution reaction (HER) is a key reaction in water splitting, and developing efficient and robust non‐noble electrocatalysts for HER is still a great challenge for large‐scale hydrogen production. Herein, a vertically aligned core–shell structure grown on Ti foil with CoP nanoarray as a core and N,P‐doped carbon (NPC) as a shell (CoP/NPC/TF) is first reported as an efficient electrocatalyst for HER. Results indicate that CoP/NPC/TF only demands the overpotentials of 91 and 80 mV to drive the current density of 10 mA cm?2 in acidic and alkaline solutions. The electrochemical measurements and theoretical calculations show that the synergy of CoP nanorod core and porous NPC shell enhances HER performance significantly, because the introduction of porous NPC shell not only offers more active sites but also improves the electrical conductivity and durability of the sample in acidic and alkaline solutions. Density functional theory calculation further reveals that all the C atoms between N and P atoms in CoP/NPC are the most efficient active sites, which greatly improve the HER performance. The identification of active species in this work provides an effective strategy to design and synthesize the low‐cost, high‐efficient, and robust CoP‐based electrocatalysts.  相似文献   

14.
Electrocatalytic water splitting is one of the sustainable and promising strategies to generate hydrogen fuel but still remains a great challenge because of the sluggish anodic oxygen evolution reaction (OER). A very effective approach to dramatically decrease the input cell voltage of water electrolysis is to replace the anodic OER with hydrazine oxidation reaction (HzOR) due to its lower thermodynamic oxidation potential. Therefore, developing the low‐cost and efficient HzOR catalysts, coupled with the cathodic hydrogen evolution reaction (HER), is tremendously important for energy‐saving electrolytic hydrogen production. Herein, a new‐type of copper–nickel nitride (Cu1Ni2‐N) with rich Cu4N/Ni3N interface is rationally constructed on carbon fiber cloth. The 3D electrode exhibits extraordinary HER performance with an overpotential of 71.4 mV at 10 mA cm?2 in 1.0 m KOH, simultaneously delivering an ultralow potential of 0.5 mV at 10 mA cm?2 for HzOR in a 1.0 m KOH/0.5 m hydrazine electrolyte. Moreover, the electrolytic cell utilizing the synthesized Cu1Ni2‐N electrode as both the cathode and anode display a cell voltage of 0.24 V at 10 mA cm?2 with an excellent stability over 75 h. The present work develops the promising copper–nickel‐based nitride as a bifunctional electrocatalyst through hydrazine‐assistance for energy‐saving electrolytic hydrogen production.  相似文献   

15.
It is demonstrated that amorphous cobalt boride (Co2B) prepared by the chemical reduction of CoCl2 using NaBH4 is an exceptionally efficient electrocatalyst for the oxygen evolution reaction (OER) in alkaline electrolytes and is simultaneously active for catalyzing the hydrogen evolution reaction (HER). The catalyst achieves a current density of 10 mA cm?2 at 1.61 V on an inert support and at 1.59 V when impregnated with nitrogen‐doped graphene. Stable performance is maintained at 10 mA cm?2 for at least 60 h. The optimized catalyst, Co2B annealed at 500 °C (Co2B‐500) evolves oxygen more efficiently than RuO2 and IrO2, and its performance matches the best cobalt‐based catalysts reported to date. Co2B is irreversibly oxidized at OER conditions to form a CoOOH surface layer. The active form of the catalyst is therefore represented as CoOOH/Co2B. EXAFS observations indicate that boron induces lattice strain in the crystal structure of the metal, which potentially diminishes the thermodynamic and kinetic barrier of the hydroxylation reaction, formation of the OOH* intermediate, a key limiting step in the OER.  相似文献   

16.
A conventional water electrolyzer consists of two electrodes, each of which is embedded with a costly and rare electrocatalyst, typically IrO2/C for oxygen evolution reaction (OER) and Pt/C for hydrogen evolution reaction (HER), respectively. HER and OER electrocatalysts usually require very different pH values to keep them stable and active. Thus, the development of earth‐abundant nonprecious metal catalysts for both HER and OER is of great importance to practical applications. This work reports the results of integrated water electrolysis using the hybrids of electrospun La0.5(Ba0.4Sr0.4Ca0.2)0.5Co0.8Fe0.2O3–δ (L‐0.5) perovskite nanorods attached to reduced graphene oxide (rGO) nanosheets as bifunctional electrodes. Via rationalizing the composition and morphology of L‐0.5/rGO nanohybrids, excellent catalytic performance and stability toward OER and HER are achieved in alkaline media. The operating voltage of integrated L‐0.5/rGO electrolyzer is tested to be 1.76 V at 50 mA cm–2, which is close to that of the commercially available IrO2/C‐Pt/C couple (1.76 V @ 50 mA cm–2). Such a bifunctional electrocatalyst could be extended toward practical electrolysis use with low expanse and high efficiency. More generally, the protocol described here broadens our horizons in terms of the designs and the diverse functionalities of catalysts for use in various applications.  相似文献   

17.
Water splitting requires development of cost‐effective multifunctional materials that can catalyze both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) efficiently. Currently, the OER relies on the noble‐metal catalysts; since with other catalysts, its operation environment is greatly limited in alkaline conditions. Herein, an advanced water oxidation catalyst based on metallic Co9S8 decorated with single‐atomic Mo (0.99 wt%) is synthesized (Mo‐Co9S8@C). It exhibits pronounced water oxidization activity in acid, alkali, and neutral media by showing positive onset potentials of 200, 90, and 290 mV, respectively, which manifests the best Co9S8‐based single‐atom Mo catalyst till now. Moreover, it also demonstrates excellent HER performance over a wide pH range. Consequently, the catalyst even outperforms noble metal Pt/IrO2‐based catalysts for overall water splitting (only requiring 1.68 V in acid, and 1.56 V in alkaline). Impressively, it works under a current density of 10 mA cm?2 with no obvious decay during a 24 h (0.5 m H2SO4) and 72 h (1.0 m KOH) durability experiment. Density functional theory (DFT) simulations reveal that the synergistic effects of atomically dispersed Mo with Co‐containing substrates can efficiently alter the binding energies of adsorbed intermediate species and decrease the overpotentials of the water splitting.  相似文献   

18.
Despite the exciting achievements made in synthesis of monofunctional electrocatalysts for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), or hydrogen evolution reaction (HER), it is challenging to develop trifunctional electrocatalysts for both ORR/OER/HER. Herein, N, O‐codoped graphene nanorings‐integrated boxes (denoted NOGB) are crafted via high‐temperature pyrolysis and following acid etching of hybrid precursors containing polymers and Prussian blue analogue cubes. The electrochemical results signified that the resulting NOGB‐800 (800 refers to pyrolysis temperature) is highly active for trifunctional electrocatalysis of ORR/OER/HER. This can be reasonably attributed to the advanced nanostructures (i.e., the hierarchically porous nanostructures on the hollow nanorings) and unique chemical compositions (i.e., N, O‐codoped graphene). More attractively, the rechargeable Zn–air battery based on NOGB‐800 displays maximum power density of 111.9 mW cm?2 with small charge–discharge potential of 0.72 V and excellent stability of 30 h, comparable with the Pt/C+Ir/C counterpart. The NOGB‐800 could also be utilized as bifunctional electrocatalysts for overall water splitting to yield current density of 10 mA cm?2 at a voltage of 1.65 V, surpassing most reported electrocatalysts. Therefore, the NOGB‐800 is a promising candidate instead of precious metal–based electrocatalysts for the efficient Zn–air battery and water splitting.  相似文献   

19.
Currently, it is still a significant challenge to simultaneously boost various reactions by one electrocatalyst with high activity, excellent durability, as well as low cost. Herein, hybrid trifunctional electrocatalysts are explored via a facile one‐pot strategy toward an efficient oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The catalysts are rationally designed to be composed by FeCo nanoparticles encapsuled in graphitic carbon films, Co2P nanoparticles, and N,P‐codoped carbon nanofiber networks. The FeCo nanoparticles and the synergistic effect from Co2P and FeCo nanoparticles make the dominant contributions to the ORR, OER, and HER activities, respectively. Their bifunctional activity parameter (?E) for ORR and OER is low to 0.77 V, which is much smaller than those of most nonprecious metal catalysts ever reported, and comparable with state‐of‐the‐art Pt/C and RuO2 (0.78 V). Accordingly, the as‐assembled Zn–air battery exhibits a high power density of 154 mW cm?2 with a low charge–discharge voltage gap of 0.83 V (at 10 mA cm?2) and excellent stability. The as‐constructed overall water‐splitting cell achieves a current density of 10 mA cm?2 (at 1.68 V), which is comparable to the best reported trifunctional catalysts.  相似文献   

20.
Large-scale application of alkaline water electrolysis for high-rate hydrogen production is severely hindered by high electricity cost, mainly due to difficulties to acquire cost-effective catalytic electrodes with both extremely low overpotential and long-term durability at ultrahigh current densities (≥1 A cm−2). Here it is demonstrated that by adopting a synthetic method of laser direct writing in liquid nitrogen via a commercial laser welding machine, a remarkably efficient and durable electrode with large area and low platinum content is obtained, where PtNi nanocatalysts with dislocation network are firmly welded on a nickel foam (NF). The dense dislocation network not only improves intrinsic activity of a majority of surface-active sites induced by coupled compressive-tensile strains synergistically promoting both Volmer and Tafel steps of alkaline hydrogen evolution reaction (HER), but also well stabilizes surface dislocations for HER at ultrahigh current densities. Such a robust electrode achieves record-low overpotentials of 5 and 63 mV at 10 and 1000 mA cm−2 in alkaline medium, respectively, exhibiting negligible activity decay after 300 h chronoamperometric test at 1 A cm−2. It displays a high Pt mass activity 16 times higher than 20 wt% Pt/C loaded on NF, surpassing most of the recently reported efficient Pt-based catalysts.  相似文献   

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