Home Journals Articles Updates About
CN
image
收藏切换
B and Fe co-doped Co2P hollow nanocubes for nitrate electroreduction to ammonia
收藏切换
PDF
Jing Miaoa, Qingling Hongb, Liping Lianga, Guomin Lia, Zhihong Liu*, c, Shibin Yin*, d, Yu Chen*, b
Chinese Chemical Letters | 2024, 35(2) : 108935
Less
收藏切换
Chinese Chemical Letters | 2024, 35(2): 108935
• Communication •
B and Fe co-doped Co2P hollow nanocubes for nitrate electroreduction to ammonia
Full
Jing Miaoa, Qingling Hongb, Liping Lianga, Guomin Lia, Zhihong Liu*, c, Shibin Yin*, d, Yu Chen*, b
Affiliations
  • a School of Materials Science and Engineering, Taiyuan University of Science and Technology, Taiyuan 030024, China
  • b School of Materials Science and Engineering, Shaanxi Normal University, Xi'an 710062, China
  • c School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062, China
  • d Guangxi Key Laboratory of Electrochemical Energy Materials, School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China
Published: 2024-02-15 doi: 10.1016/j.cclet.2023.108935
Outline
收藏切换

Nitrate (NO3−) electroreduction reaction (NO3−RR) provides an attractive and sustainable route for NO3− pollution mitigation or energy-saved ammonia (NH3) synthesis. In this work, high-quality B and Fe co-doped Co2P hollow nanocubes (B/Fe-Co2P HNCs) are successfully synthesized though simultaneous boronation-phosphorization treatment, which reveal outstanding selectivity, activity, stability for the NO3− to NH3 conversion in neutral electrolyte because of big surface area, fast mass transport, superhydrophilic surface, and optimized electronic structure. B/Fe-Co2P HNCs can achieve the high NH3 yield rate (22.67 mg h−1 mgcat−1) as well as Faradaic efficiency (97.54%) for NO3−RR, greatly outperforming most of non-precious metal based NO3−RR electrocatalysts.

Nitrate electroreduction reaction  /  Ammonia synthesis  /  Transition metal phosphides  /  Hollow nanocubes
Jing Miao, Qingling Hong, Liping Liang, Guomin Li, Zhihong Liu, Shibin Yin, Yu Chen. B and Fe co-doped Co2P hollow nanocubes for nitrate electroreduction to ammonia[J]. Chinese Chemical Letters, 2024 , 35 (2) : 108935 - . DOI: 10.1016/j.cclet.2023.108935
Full Text
Less
Ammonia (NH3) not only acts as a critical industrial raw chemical in the agriculture, textile, pharmaceutical and plastic industries, but also serves as an emissions-less and efficient energy carrier [1,2]. Compared with the traditional Haber-Bosch process at high pressures and high temperatures, the electrochemical synthesis method can provide an environmentally friendly and energy-efficient approach for large-scale NH3 production [3]. At present, nitrogen electroreduction reaction suffer from the highly stable N≡N triple bond (ca. 941 kJ/mol) as well as unsatisfactory Faradaic efficiency [4]. In contrast, the nitrate (NO3−) electroreduction reaction (NO3−RR) is considered as an attractive electrochemical method for NH3 production because of the high solubility of NO3− in water and the small dissociation energy of N═O double bond (ca. 204 kJ/mol) [5-7]. In fact, NO3− pollution in drinking water causes severe problems to human health, which mainly originates from the excessive use of nitrogen-containing fertilizer and the improper discharge of wastewater [8,9]. From the energy-saving and environmental protection perspectives, thus, NO3−RR is highly attractive to harness NO3− contamination to produce valuable NH3. However, the competing hydrogen evolution reaction (HER) and complex eight-electron transfer process may lead to the low NH3 yield and selectivity [10,11].
Recently, transition metal phosphides (TMPs) are attractive electrocatalyst because of their low-cost, impressive activity and positive reduction potential for NO3–RR [12-14]. To achieve high activity, selectivity, and durability of TMPs electrocatalysts for NO3–RR, many efforts have been devoted to exquisitely control their morphology, optimize their chemical composition, and modify their electronic structure [15,16]. For example, Li and co-workers successfully synthesized Fe-doped CoP nanohoops, which revealed improved NO3–RR activity compared to CoP nanohoops due to electronic regulation function of Fe atoms [17]. Among various nanostructures with different morphologies, hollow nanostructures can offer great benefits for boosting their electrocatalytic performance, which efficiently provide more exposed active sites and shorten the charge transport pathways [18-21]. In additional, boron (B) doping is an efficient approach to boost the intrinsic activity of transition element-based nanostructures for various electrocatalytic reactions, such as B-doped Fe7S8/FeS2 electrocatalysts for alkaline HER [22], B doped cobalt oxide nanocrystals for oxygen evolution reaction [23], and B, P co-doped Pd nanothorn arrays for NO3−RR [24]. Mainly, B atoms can well rearrange the inhomogeneous spin and charge density of metal atoms, originating from the easy coordination with metal atoms [25]. Inspired by this, it is highly desired to synthesize B-doped porous TMPs nanostructures for the NO3–RR.
In this work, we successfully synthesized B and Fe co-doped Co2P hollow nanocubes (B/Fe-Co2P HNCs) and further investigated the NO3–RR performance. The introduction of electron-deficient B atoms could efficiently rearrange the electronic structure of Fe-Co2P HNCs. Besides, the hollow and porous architecture could provide high surface area, abundant active sites and available mass transfer pathways. Benefiting from the hollow nanostructures, well-defined void space, and tunable chemical compositions, B/Fe-Co2P HNCs exhibited an outstanding selectivity, activity, stability for the NO3– to NH3 conversion in neutral Na2SO4 electrolyte. B/Fe-Co2P HNCs with long-term stability and high activity provide a facile strategy for synthesis NH3 and elimination of NO3− contamination.
B/Fe-Co2P HCNs were synthesized though successive precipitation transformation and boronation-phosphidation methods, as illustrated in Scheme 1. Prussian blue analogues (PBAs) are recognized as popular precursor for TMPs synthesis because of their tunable chemical composition, large specific surface areas, and high porosity [26].
First, CoFe-PBA HNCs were easily synthesized through coprecipitation method (see experimental section in Supporting information for the detail). Both the scanning electron microscopy (SEM) and transmission electron microscopy (TEM) characterization show that CoFe-PBA HNCs have a well-defined cubic morphology, uniform size (ca. 300–400 nm) and smooth surface (Fig. S1 in Supporting information). In X-ray diffraction (XRD) characterization, all diffraction peaks are well indexed to K2CoFe(CN)6 crystal (JCPDS No. 75–0038) (Fig. S2 in Supporting information). Thus, SEM and XRD characterization confirm the successful synthesis of CoFe-PBA HNCs. After simultaneous boronation-phosphorization process, the energy dispersive X-ray (EDX) characterization displays the co-existence of B, Fe, Co and P elements whereas K and N elements of PBA are not observed (Fig. 1a). The XRD pattern of as-prepared sample matches well with Co2P crystal (JCPDS No. 32–0306) and the characteristic peak of PBA precursor disappear completely (Fig. 1b). Thus, we can be concluded that PBA is completely converted into B/Fe-Co2P HNCs. For comparison, Fe-Co2P HNCs without B-doping were synthesized by phosphorization treatment (Fig. S3 in Supporting information). Compared with Fe-Co2P HNCs, the main diffraction peaks of B/Fe-Co2P HNCs shift positively, which can be attributed to B doping [27,28]. According to nitrogen adsorption-desorption test, the surface area of B/Fe-Co2P HNCs is 42.4 m2/g (Fig. 1c), suggesting that the hollow porous B/Fe-Co2P HNCs can offer ample accessible active sites. Meanwhile, B/Fe-Co2P HNCs show a smaller contact angle compared to Fe-Co2P HNCs (Fig. 1d), indicating that the introduction of B atoms can provide superhydrophilic surface. The superhydrophilic surface can facilitate electrolyte adsorption and electron transfer processes [24].
The hard template strategy can generally preserve the initial morphology of precursor. During the boronation-phosphorization process, CoFe-PBA HNCs are easily decomposed into lesser broken cubes with the rough and porous feature, indicating that CoFe-PBA HNCs are successfully converted into B/Fe-Co2P HNCs (Figs. 2a and b). By adjusting the mass ratio of B and P, B/Fe-Co2P HNCs with different B/P mass ratio can also be obtained (Fig. S4 in Supporting information). TEM image clearly reveals the regular and large interior spaces within ultrafine nanoparticles embedded in the outer face (Fig. 2c). High-resolution TEM image distinctly reveals the lattice fringes of 0.175 and 0.221 nm (Fig. 2d), corresponding to (020) and (112) planes of Co2P [29,30]. Elemental mapping characterization shows that Co, P, B, and Fe elements are homogeneously distributed on the nanocubes (Fig. 2e), confirming the B and Fe co-doping, again.
The surface component and valence state of B/Fe-Co2P HNCs were examined by X-ray photoelectron spectroscopy (XPS). In the Co 2p spectrum (Fig. 3a), the peaks at 795.5 and 780.1 eV correspond to 2p1/2 and 2p3/2 orbits of Co2+ species, and the peaks at 797.2 and 782.1 eV are attributed to 2p1/2 and 2p3/2 orbits of Co3+ species. The two broad peaks at 785.6 and 802.5 eV are assigned to the satellite peaks [31,32]. In the Fe 2p spectrum (Fig. 3b), two peaks at 724.5 and 710.7 eV can be ascribed to 2p1/2 and 2p3/2 orbits of Fe2+ species, whereas the peaks at 727.6 and 713.3 eV correspond to 2p1/2 and 2p3/2 orbits of Fe3+ species, along with two shakeup satellite peaks at 717.7 and 733.3 eV [33,34]. Particularly, the binding energies of Co 2p and Fe 2p negatively shift after B doping (Fig. S5 in Supporting information), suggesting the electron interaction between metal atom and B atom because of the electron-deficient nature of B [35,36]. In the B 1s spectrum (Fig. 3c), the peak at 187.8 eV correspond to the peak of metallic B [37]. The peaks at higher binding energy (194.8 eV, 196.2 eV) correspond to the oxidic boron species [38,39]. In the P 2p spectrum (Fig. 3d), the huge peak of 133.9 eV belongs to P-O, and the two peaks at 129.3 and 130.4 eV can be ascribed to TMPs, which is constant with reported TMPs nanostructures [40,41].
The NO3–RR performance of B/Fe-Co2P HNCs and Fe-Co2P HNCs were investigated in 0.5 mol/L Na2SO4 electrolyte with and without 50 mmol/L NaNO3. Both Fe-Co2P HNCs and B/Fe-Co2P HNCs display an obvious electroactivity for NO3−RR, reflecting the cathodic current markedly increases after the addition of NO3− into 0.5 mol/L Na2SO4 electrolyte. Compared with Fe-Co2P HNCs without B doping, B/Fe-Co2P HNCs exhibit a more positive onset potential and a bigger reduction peak current density for NO3–RR, implying the outstanding NO3−RR catalytic activity (Fig. 4a). This phenomenon further suggests that the intrinsic NO3−RR activity of Fe-Co2P HNCs is significantly enhanced after B doping. Since XPS measurements show the introduction of B atoms can efficiently regulate the electronic structure of Fe-Co2P HNCs, the electronic effect is responsible for intrinsic activity enhancement of Fe-Co2P HNCs due to B doping. Among B/Fe-Co2P HNCs with different B/P ratio, B/Fe-Co2P HNCs (B: P = 2:1) has the highest NO3–RR (Fig. S6 in Supporting information), which in turn confirms that both B and P atoms have obvious influence on NO3–RR activity enhancement. To study the activity and selectivity of B/Fe-Co2P HNCs for NO3–RR, the reactant and reductive products were determined by the chronoamperometry tests at various applied potentials. After chronoamperometry tests for 3 h, colorimetric methods were used to quantity the NH3 yields and Faradaic efficiency (Figs. S7 and S8 in Supporting information). Upon varying the applied potential from −0.5 V to −0.9 V (vs. RHE), the NH3 production rate and conversion rate of NO3–RR at B/Fe-Co2P HNCs gradually increase, while the Faradaic efficiency of NH3 at B/Fe-Co2P HNCs displays a volcanic shape (Fig. 4b), similar to Fe-Co2P HNCs (Fig. S9 in Supporting information). Compared with Fe-Co2P HNCs, B/Fe-Co2P HNCs displays larger NH3 production rate and Faradaic efficiency under same potential. For example, B/Fe-Co2P HNCs can achieve the NH3 yield of 22.67 mg h−1 mgcat−1 and the Faradaic efficiency of 97.54% at −0.70 V potential (Fig. 4c), much higher than that of Fe-Co2P HNCs, suggesting high activity and selectivity of B/Fe-Co2P HNCs for the NO3− to NH3 conversion. The control experiment performed in 0.5 mol/L Na2SO4 electrolyte only generates negligible NH3, excluding the interference of catalysts and environmental contaminants (Fig. S10 in Supporting information). Impressively, B/Fe-Co2P HNCs have higher NH3 yield and Faradaic efficiency than most previously reported non-precious metal electrocatalysts for NO3–RR (Table S1 in Supporting information), further demonstrating the high electroactivity of B/Fe-Co2P HNCs. Electrochemical impedance spectroscopy (EIS) characterization displays that the charge transfer resistance of NO3−RR at B/Fe-Co2P HNCs (49.3 Ω) is much smaller than that at Fe-Co2P HNCs (125 Ω), suggesting that the B doping accelerates the reaction kinetics of NO3–RR (Fig. 4d) [24].
Benefiting from the small particle size and porous structure, B/Fe-Co2P HNCs can provide a high surface area and expose affluent active sites, facilitating the NO3− to NH3 conversion [42,43]. The electrochemical double-layer capacitances (Cdl) are estimated via cycling voltammetry (CV) curves under different scan rates (Fig. S11 in Supporting information). The Cdl value (22.41 mF/cm2) of B/Fe-Co2P HNCs is close to that of Fe-Co2P HNCs (21.87 mF/cm2), indicating that the electrochemical active surface area of B/Fe-Co2P HNCs is close to that of Fe-Co2P HNCs. Thus, the area effect is not a main factor for activity enhancement of B/Fe-Co2P HNCs. In fact, the doped B atoms can act as Lewis acid active sites to better adsorb NO3–, which accelerates the electroreduction of NO3– to NH3 [23,44]. Meanwhile, B/Fe-Co2P HNCs show a smaller contact angle compared to Fe-Co2P HNCs, indicating that the introduction of B atoms can provide superhydrophilic surface [45]. Additionally, B doping can effectively optimize the charge density and redistribute the inhomogeneous spin, which is favorable for adsorption kinetics and reduce the reaction energy barrier during NO3–RR [46,47]. As a result, B/Fe-Co2P exhibits extremely outstanding NO3–RR electroactivity.
Furthermore, the durability of B/Fe-Co2P HNCs was investigated by chronoamperometry test. Chronoamperometric curve reveals that B/Fe-Co2P HNCs can be sustained for 30 h with negligible decay during NO3–RR, revealing the excellent stability and practical application for electrochemical NH3 production (Fig. 5a). After long-time electrolysis, EDX, XRD and TEM characterizations display that chemical composition, morphology and structure remain nearly unchanged, revealing stability of B/Fe-Co2P toward NO3–RR (Figs. 5b-d).
In summary, we have rationally designed and synthesized B/Fe-Co2P HCNs with an open structure and unique hollow interior. Thanks to superhydrophilic surface and abundant active sites, the obtained B/Fe-Co2P HCNs show excellent electrocatalytic activity for NO3– to NH3 conversion. B/Fe-Co2P HCNs show an impressive NH3 production rate of 22.67 mg h−1 mgcat−1 and Faradaic efficiency of 97.54%, much superior to the most reported non-precious metal NO3–RR electrocatalysts in neutral media. This work not only highlights a new boronation-phosphorization way for the nanomaterials synthesis but also points out the high-performance of B/Fe-Co2P HCNs for NO3– removal and NH3 synthesis.
Declaration of competing interest
Less
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
Less
This work is supported by Natural Science Foundation of Shanxi Province (No. 202203021222213), Taiyuan University of Science and Technology Scientific Research Initial Funding (No. 20222091), National Natural Science Foundation of China (No. 22073061), Science and Technology Innovation Team of Shaanxi Province (No. 2023-CX-TD-27), Fundamental Research Funds for the Central Universities (No. GK202202001).
Supplementary materials
Less
Supplementary material associated with this article can be found, in the online version, at doi:10.1016/j.cclet.2023.108935.
References
Less
[1]
D.F. Qi, F. Lv, T.R. Wei, et al., Nano Res. Energy 1 (2022) e9120022.
[2]
Z.B. Yao, S.Q. Liu, H.H. Liu, et al., Adv. Funct. Mater. 33 (2022) 2209843.
[3]
J. Liang, Q. Liu, A.A. Alshehri, et al., Nano Res. Energy 1 (2022) e9120010.
[4]
Y.M. Huang, J. Long, Y.T. Wang, et al., ACS Appl. Mater. Interfaces 13 (2021) 54967–54973.
[5]
Z.X. Ge, T.J. Wang, Y. Ding, et al., Adv. Energy Mater. 12 (2022) 2103916.
[6]
Y. Xu, M.Z. Wang, K.L. Ren, et al., J. Mater. Chem. A 9 (2021) 16411–16417.
[7]
Q.L. Hong, B.Q. Miao, T.J. Wang, et al., Energy Lab 1 (2023) 220022.
[8]
Y.T. Wang, W. Zhou, R.R. Jia, et al., Angew. Chem. Int. Ed. 59 (2020) 5350–5354.
[9]
Q. Li, Y.N. Liu, Z. Wan, et al., Chin. Chem. Lett. 33 (2022) 3835–3841.
[10]
Q.F. Yao, J.B. Chen, S.Z. Xiao, et al., ACS Appl. Mater. Interfaces 13 (2021) 30458–30467.
[11]
J.M. Cai, Y.Y. Wei, A. Cao, et al., Appl. Catal. B: Environ. 316 (2022) 121683.
[12]
G.L. Wen, J. Liang, Q. Liu, et al., Nano Res. 15 (2022) 9972–9977.
[13]
Q.L. Hong, J. Zhou, Q.G. Zhai, et al., Chem. Commun. 57 (2021) 11621–11624.
[14]
C.M. Li, D.Q. Zhu, S.S. Cheng, et al., Chin. Chem. Lett. 33 (2022) 1141–1153.
[15]
S.H. Ye, Z.D. Chen, G.K. Zhang, et al., Energy Environ. Sci. 15 (2022) 760.
[16]
S.L. Chen, H. Jang, J. Wang, et al., J. Mater. Chem. A 8 (2020) 2099.
[17]
Q.L. Hong, Z.N. Zhang, X.H. Wang, et al., Inorg. Chem. 61 (2022) 4397–14402.
[18]
N.Y. Wei, M.Y. Mao, J. Wu, et al., Fuel 319 (2022) 123637.
[19]
M.X. Chen, F.T. Kong, H.L. Yao, et al., Chem. Eng. J. 45 (2023) 139820.
[20]
Y. Wang, Y.Z. Wang, H.W. Gao, et al., Chem. Eng. J. 451 (2023) 138515.
[21]
Y.L. Yang, Y.R. Wang, G.K. Gao, et al., Chin. Chem. Lett. 33 (2022) 1439–1444.
[22]
J. Wu, Q. Zhang, K. Shen, et al., Adv. Funct. Mater. 32 (2022) 2107802.
[23]
M.Q. Yu, C. Weidenthaler, Y. Wang, et al., Angew. Chem. Int. Ed. 61 (2022) e202211543.
[24]
Y. Xu, Y.W. Sheng, M.Z. Wang, et al., J. Mater. Chem. A 1 (2022) 16290.
[25]
K. Deng, W.X. Wang, Q.Q. Mao, et al., Small 18 (2022) 2203020.
[26]
G.X. Zhang, Y.L. Li, X. Xiao, et al., Nano Lett. 21 (2021) 3016–3025.
[27]
S.H. Wang, P. Wang, X.F. Sun, et al., Appl. Catal. B: Environ. 297 (2021) 120386.
[28]
Y. Lin, K. Sun, X.M. Chen, et al., J. Energy Chem. 55 (2021) 92–101.
[29]
Y. Xu, J. Mo, J.F. Long, et al., J. Energy Chem. 73 (2022) 322–329.
[30]
X.J. Zhao, T.Q. Gao, W.H. Ren, et al., J. Energy Chem. 75 (2022) 250–259.
[31]
Q. Liu, L.S. Xie, J. Liang, et al., Small 18 (2022) 2106961.
[32]
Y. Jia, Y.G. Ji, Q. Xue, et al., ACS Appl. Mater. Interfaces 13 (2021) 45521–45527.
[33]
J. Miao, X.J. Zhao, H.Y. Hu, et al., ACS Appl. Nano Mater. 5 (2022) 4948–4957.
[34]
Q.M. Chen, Q.C. Zhang, H.B. Liu, et al., Small 17 (2021) 2007858.
[35]
F.L. Gou, H. Wang, M.M. Fu, et al., Appl. Surf. Sci. 612 (2023) 155872.
[36]
Y.H. Li, H.J. Yu, Z.Q. Wang, et al., Chem. Commun. 55 (2019) 14745–14748.
[37]
Z.Q. Wang, M. Li, P. Wang, et al., Chem. Eng. J. 449 (2022) 137771.
[38]
F.G. Wang, B. Liu, H.Y. Wang, et al., J. Colloid Interface Sci. 610 (2022) 173–181.
[39]
W.J. Jiang, S. Niu, T. Tang, et al., Angew. Chem. Int. Ed. 56 (2017) 1–7.
[40]
G. Ma, N. Yang, Y.F. Xue, et al., ACS Appl. Mater. Interfaces 13 (2021) 42763–42772.
[41]
J. Wang, H. Cheng, S.Y. Ren, et al., J. Mater. Chem. A 8 (2020) 16018–16023.
[42]
X.Y. Zhang, G. Ma, L.L. Shui, et al., Chem. Eng. J. 430 (2022) 132666.
[43]
H.Y. Zhou, B.Y. Xiong, L.S. Chen, et al., J. Mater. Chem. A 8 (2020) 20286.
[44]
B. Chang, L.L. Li, D. Shi, et al., Appl. Catal. B: Environ. 283 (2021) 119622.
[45]
R.Q. Guo, J.L. Shi, K.W. Ma, et al., J. Colloid Interface Sci. 651 (2023) 172–181.
[46]
B.B. Fan, H.Z. Wang, H. Zhang, et al., Adv. Funct. Mater. 32 (2022) 2110783.
[47]
F.G. Wang, B. Li, Z.Y. Lin, et al., Appl. Surf. Sci. 592 (2022) 153245.
Appendix
Less
Year 2024 volume 35 Issue 2
PDF
52
29
Cite this Article
BibTeX
Article Info
doi: 10.1016/j.cclet.2023.108935
  • Receive Date：2023-06-08
  • Online Date：2025-11-20
  • Published：2024-02-15
Article Data
Affiliations
History
  • Received：2023-06-08
  • Revised：2023-08-12
  • Accepted：2023-08-15
Affiliations
    a School of Materials Science and Engineering, Taiyuan University of Science and Technology, Taiyuan 030024, China
    b School of Materials Science and Engineering, Shaanxi Normal University, Xi'an 710062, China
    c School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062, China
    d Guangxi Key Laboratory of Electrochemical Energy Materials, School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China
References
Share
https://castjournals.cast.org.cn/joweb/ccl/EN/10.1016/j.cclet.2023.108935
Share to
QR

Scan QR to access full text

Cite this article
BibTeX
Citations
表12种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
关闭全屏
  • BibTeX
  • EndNote
  • RefWorks
  • TxT
Links
Articles
Latest Articles
Most Read
Collections
Updates
Events
News
Multimedia
About
About Us
Contact
No. 86 Xueyuan South Road, Haidian District, Beijing
100081
010-62199257
qkjq@cast.org.cn

Copyright © 2025 China Association for Science and Technology. All rights reserved. For all open access content, the relevant licensing terms apply.
Sponsored by the Office of the Leading Group for Cybersecurity and Informatization of CAST, and supported by Science and Technology Review Publishing House