PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
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2023
·Vol. 120
·期 44
·e2307320120
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IF 11.1
Yangyang Yu,Ye He,Ping Yan,Shengyao Wang,Fan Dong
The selective photocatalytic conversion of CO2 and H2O to high value-added C2H4 remains a great challenge, mainly attributed to the difficulties in C–C coupling of reaction intermediates and desorption of C2H4* intermediates from the catalyst surface. These two key issues can be simultaneously overcome by alloying Ag with Cu which gives enhanced activity to both reactions. Herein, we developed a facile stepwise photodeposition strategy to load Cu–Ag alloy sub-nanoclusters (ASNCs) on TiO2 for CO2 photoreduction to produce C2H4. The optimized catalyst exhibits a record-high C2H4 formation rate (1110.6 ± 82.5 μmol g−1 h−1) with selectivity of 49.1 ± 1.9%, which is an order-of-magnitude enhancement relative to current work for C2H4 photosynthesis. The in situ FT-IR spectra combined with DFT calculations reveal the synergistic effect of Cu and Ag in Cu–Ag ASNCs, which enable an excellent C–C coupling capability like Ag and promoted C2H4* desorption property like Cu, thus advancing the selective and efficient production of C2H4. The present work provides a deeper understanding on cluster chemistry and C–C coupling mechanism for CO2 reduction on ASNCs and develops a feasible strategy for photoreduction CO2 to C2 fuels or industrial feedstocks.
研究领域:
化学
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材料科学
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环境科学
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产品关联
DOI
PubMed
高影响因子
Inorganic Chemistry Frontiers
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2025
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IF 6.4
Qin Zhang,Jiancong Liu,Dongxu Wang,Chengxu Jin,Li Fang,Xingyu Li,Yingjie Jiang,Xin Wang,Chungui Tian
The construction of strong metal-support interaction (SMSI) between ultrasmall metal nanoparticles and semiconductor supports remains a pivotal challenge in developing high-performance photocatalysts for selective CO2 conversion. Herein, we propose a coordination-induced in-situ confinement strategy that synchronously achieves high dispersion of small-sized Ag nanoparticles (Ag NPs) and SMSI with ultrathin C3N4. Through melamine-mediated Ag-N coordination bonds, this approach orchestrates three synergistic effects: (1) Coordination-induced confinement of Ag NPs (~3.3 nm) via covalent Ag-N linkages, yielding an increase in active site density and stability compared to conventional Ag/C3N4; (2) Enhanced electron transfer from C3N4 to Ag, extending carrier lifetimes and suppressing charge recombination; (3) Interfacial electronic redistribution that promotes the generation of *COOH intermediates, steering the reaction pathway toward CO with high selectivity. Furthermore, the coordination-induced thermal condensation induces nitrogen vacancies in C3N4, which act as molecular traps to enhance CO2 adsorption capacity and synergize with Ag sites for efficient CO2 activation. As a result, the optimized catalyst exhibits a remarkable CO yield of 70.63 μmol·g-1·h-1 without the use of sacrificial agents, along with high selectivity (> 98 %) and excellent stability. This work establishes a universal paradigm for engineering metal-semiconductor interfaces through coordination chemistry, offering transformative insights into solar-driven CO2-to-fuel conversion technologies.
研究领域:
材料科学
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环境科学
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化学工程
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2025
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IF 21.1
Yong Yang,Jianfeng Jiang,Ya-Nan Feng,Zanyong Zhuang,Fei-Fei Chen,Dantong Zhang,Yan Yu
The strong CO 2 adsorption and facile CO desorption are a trade-off issue for CO 2 -to-CO photoreduction pathways. Synchronous optimization of these two steps remains a substantial hurdle and has been less explored. Herein, an O/N mixed coordinated Co-NTA (NTA: nitrilotriacetic acid), featuring an ultralong nanofiber architecture, is reported for efficient CO 2 photoreduction. The mixed coordination can regulate the positions of d -band center of Co sites and also d – p orbital coupling with coordination atoms, which are recognized as main activity descriptors. Consequently, free energies of both steps of CO 2 →*CO 2 and *CO→CO are well optimized, making the CO 2 -to-CO photoreduction pathways more favorable thermodynamically. By contrast, the classic N-coordinated Co-MeIm (MeIm: 2-methylimidazole) and O-coordinated Co-BDC (BDC: 1,4-benzenedicarboxylic acid) suffer from unfavorable CO 2 adsorption and intractable CO desorption, respectively. In addition, achiral NTA molecules can direct the growth of Co-NTA into one-dimensional (1D) nanofibers, while Co-BDC and Co-MeIm possess typical 2D nanosheet and 3D polyhedron architectures. The fast electron transport along the axis directions makes charge-transfer kinetics most efficient over 1D Co-NTA. The thermodynamic and kinetic benefits jointly contribute to the 1.8-fold increase in CO production over 1D Co-NTA.
研究领域:
材料科学
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化学工程
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环境科学
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DOI
高影响因子
ACS Applied Materials & Interfaces
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2024
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IF 8.3
Yongfang Jia,Juan Gao,Feng Yang,Yangmin Diao,Qijun Liu,Yong Zhang,Hongliang Sun,Min Pan,Mei Huang,Min Xu,Xuru Duan,Yong Zhao
Despite the excellent performance of Nb3O7(OH) in dye-sensitized solar cells and catalysis, its charge separation, transport, and structural properties remain poorly understood. Herein, the Nb3O7(OH) nanorods were prepared, and their structural characteristics, optoelectronic properties, and carrier mobility were also analyzed and investigated through a series of complex characterizations. Theoretical prediction suggested that the exciton binding energy of Nb3O7(OH) could be as high as 100.49 meV. The temperature-dependent photoluminescence (PL) of Nb3O7(OH) nanorods revealed two activation energies, and a higher proportion of long-lived components observed in the photoluminescence decay indicated effective electron trapping. That is, two energy states were present, hindering photogenerated charge recombination and promoting photocatalytic action. Current–voltage characteristics of the Nb3O7(OH) nanorod film were analyzed, revealing an ultrahigh carrier mobility of ∼310 cm2/V·s, ensuring fast and efficient electron transfer. Furthermore, Nb3O7(OH) nanorods were employed to reduce CO2, resulting in the effective production of CO and CH4. Overall, considering the presence of hydroxyl pairs on the surface of Nb3O7(OH), which facilitate the formation of the frustrated Lewis acid–base pairs and the activation of CO2, together with its effective electron trapping and charge transport, give Nb3O7(OH) nanorods a promising potential for CO2 reduction.
研究领域:
材料科学
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催化化学
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光电化学
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DOI
高影响因子
INORGANIC CHEMISTRY
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2022
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IF 5.436
Zhijie Zhang,Liang Li,Ying Jiang,Jiayue Xu
Heterojunction manipulation has been deemed as a promising approach in exploring efficient photocatalysts for CO2 reduction. In this article, a novel step-scheme (S-scheme) photocatalyst of CsPbBr3 quantum dots/BiOBr nanosheets (CPB/BiOBr) was fabricated via a facile self-assembly process. The strong interaction, staggered energy band alignments, and much different Fermi levels between CsPbBr3 and BiOBr promised the formation of an S-scheme heterojunction. The resultant CPB/BiOBr heterojunction delivered remarkable photocatalytic performance in CO2 reduction, with an electron consumption rate of 72.3 μmol g–1 h–1, which was 4.1 and 5.7 times that of single CsPbBr3 and BiOBr, respectively. The superior photocatalytic performance originated from the impactful spatial separation of photoinduced electron–hole pairs, as well as the preservation of strongly reductive electrons for CO2 reduction. This work offers a rational strategy to design S-scheme heterojunctions based on lead halide perovskites, which are expected to have potential applications in the field of photocatalysis and solar energy utilization.
研究领域:
材料科学
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环境科学
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化学工程
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DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
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2024
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IF 18.5
Lulu Zhao,Huilin Hou,Shuo Wang,Lin Wang,Yang Yang,Chris R. Bowen,Jinguo Wang,Ziyi Liao,Dongjiang Yang,Ruifang Yan,Weiyou Yang
Despite the development of a range of photocatalysts for CO 2 reduction, the practical applications are significantly limited by low conversion efficiencies and their reliance on sacrificial agents, which are rooted in thermodynamic and kinetic challenges related to CO 2 conversion. Here, the engineering of Co single atoms in ultrathin single-crystal BiOCl nanosheets for boosted photocatalytic CO 2 reduction is reported. The engineering of Co atoms modulates the distribution of photogenerated charges at the catalyst surface, controlling key surface reaction dynamics and suppressing surface electron-hole recombination. This modulation also improves light absorption and enhances CO 2 adsorption and activation, leading to more efficient surface reactions. Notably, CO 2 is stably adsorbed onto the (001) face of BiOCl through a Bi-O-C(= O)-Co-O coordination unit, which lowers the activation energy for CO 2 reduction and reduces the formation energy of COOH − intermediates. As a result, the BiOCl photocatalysts achieve a CO formation rate of 183.9 µmol g −1 h −1 , when irradiated with a 300 W Xe lamp without cocatalysts or sacrificial agents. It represents an ≈13-fold increase compared to that of pristine BiOCl, and surpasses most reported Bi-based photocatalysts to date. Current work provides valuable insights into engineering of single atoms for developing advanced CO 2 -reduction photocatalysts.
研究领域:
材料科学
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环境科学
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催化化学
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产品关联
DOI
高影响因子
ACS Applied Nano Materials
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2021
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IF 5.097
Zhi Liu,Jia Zheng,Lianfeng Duan,Zhi Zhu
CO2 photoreduction into high-valued fuels is considered as a promising route to alleviate the clash between the environment and energy. Morphology-dependent CeO2 nanocrystallines with special crystal planes and increased amounts of specific surface areas, structural defects, and active sites have recently demonstrated excellent performance in catalysis. In this article, a biomass-assisted synthesis of CeO2 (BC) photocatalyst is successfully synthesized via a simple yet effective hydrothermal-calcining method by using commercial Ce(NO3)3 as a precursor and leaves of Alternanthera philoxeroides (LAP) as a crystal growth modifier. The amount of LAP introduced into the precursor has a significant effect on regulating the growth of the formed CeO2 from nanocubes to nanorods for the resulting BCs. Owing to the emergence of the just right microenvironment for regulating the growth of the CeO2 nanocrystalline, the optimal sample of BC-15 with a morphology of nanorods is found to be the most efficient one as a photocatalyst for CO2 reduction under visible light. As the major product, the CO yield (126.8 μmol g–1 at a reaction time of 6 h) of BC-15 is ∼7.4-fold of the reference CeO2 nanocubes synthesized without LAP in the precursor. In addition, the underlying evolution process of the nanorods and detailed mechanism insight into the boosted CO2 photoreduction performance are investigated by means of a series of experimental characterizations and results. The present work provides a meaningful protocol to utilize the crystal phase engineering strategy to design morphology dependence of photocatalysts and assisted synthesis with renewable biomass materials for solar-to-fuel conversion.
研究领域:
材料科学
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环境科学
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能源科学
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产品关联
DOI
高影响因子
NANOTECHNOLOGY
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2020
·Vol. 31
·期 21
·215605
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IF 3.551
Yu-Wei Liu,Shao-Hong Guo,Si-Qi You,Chun-Yi Sun,Xin-Long Wang,Liang Zhao,Zhong-Min Su
Halide perovskites have been employed as photocatalysts for CO2 photoreduction due to their excellent optical properties and unique electronic structure. However, their photocatalytic performance is relatively poor. Herein, we demonstrate a new strategy with Mn-doped CsPb(Br/Cl)3 mixed-halide perovskites as catalysts to enhance the efficiency of CO2 photoreduction. By tuning the content of Mn, a series of CsPb(Br/Cl)3:Mn perovskites are obtained and show high efficiency in CO2 conversion to CO and CH4. For the optimum catalyst sample, especially, the yields of CO and CH4 reach 1917 μmol g−1 and 82 μmol g−1 which are 14.2 and 1.4 times higher than those of CsPbBr3. This work provides new insights into improving the reactivity of perovskites in CO2 photoreduction.
研究领域:
材料科学
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催化化学
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环境科学
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产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2022
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IF 16.744
Hainan Shi,Jun Du,Haozhi Wang,Zhenghao Jia,Dingfeng Jin,Jiaqi Cao,Jungang Hou,Xinwen Guo
Solar-driven CO 2 conversion into fuels is a promising solution toward green energy conversion. It is a challenge to regulate the precise structure of photocatalysts at the atomic scale, facilitating the charge transfer and improving CO 2 photoreduction performance. Herein, conductive Ti 3+ -rich TiO x clusters with unsaturated Ti–O 5 coordination incorporated into nanosheets-assembled hollow sulfide semiconductors were prepared through a versatile transformation strategy by using NH 2 -MIL-125(Ti) metal–organic–framework as precursor. This typical photocatalysts exhibit highly selective photoreduction of CO 2 , achieving a super high visible-light photocatalytic CO evolution activity of 1100 μmol g −1 h −1 . The active sites were identified on the surface of conductive TiO x clusters, inducing efficient trapping of photogenerated electrons at the interface and suppressing H 2 generation. This enhanced performance is ascribed to Ti 3+ -rich TiO x clusters as an efficient cocatalyst on sulfide semiconductor providing more active sites due to electrical conductivity and unsaturated coordination environment. This work provides a promising approach to enhance photocatalytic performance of the catalysts coupled by unique metal oxide clusters for selective photoreduction of CO 2 .
研究领域:
材料科学
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环境科学
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化学工程
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DOI
高影响因子
RENEWABLE ENERGY
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2021
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IF 8.001
Yanan Wei,Xin Li,Yunlei Zhang,Yongsheng Yan,Pengwei Huo,Huiqin Wang
Wide-light absorption performance and efficient carrier separation ability are the necessary conditions for excellent photocatalytic materials. In this research, g-C 3 N 4 QDs (CN QDs) and Au nano-particles (NPs) co-modified CeO 2 /Fe 3 O 4 micro-flowers (MFs) photocatalyst (CACeF) has been prepared. CO 2 photoreduction experiments showed that the composite had obviously enhanced photoreduction activity and photocatalytic stability. The yields of CO and CH 4 over it as catalyst in 4 h is about 5 and 8 times greater than that of pure CeO 2 . Photoelectrochemical tests showed that the heterojunction between CN QDs and Au NPs can greatly improve the carrier separation ability and the light-utilization efficiency of photocatalysts. Besides, the excellent electronic transmission performance of Au NPs provided a specific channel for the electron transmission, and the strong local surface plasmon resonance (LSPR) of Au NPs resulted in a lot of hot-electrons can directly take part in the CO 2 photoreduction. The synergistic effect between CN QDs and Au NPs can further enhance the photocatalytic activity of the photocatalyst. Fe 3 O 4 QDs can ensure the effective recovery and reuse of the composite without affecting the photocatalytic performance of composite. Finally, a potential photoreduction mechanism of CN QDs and Au NPs co-modified CeO 2 /Fe 3 O 4 MFs photocatalyst were discussed in total.
研究领域:
材料科学
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环境科学
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化学工程
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产品关联
DOI
高影响因子
FUEL
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2023
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IF 7.4
Jing Li,Tingshan Chan,Chuanyong Jing,Jin Wang
Selective conversion of CO 2 to fuels and chemicals has been considered one of the key challenges in the photocatalytic CO 2 reduction reaction. The multi-electron reduction reaction requires the design of photocatalysts that can adsorb CO 2 and transfer electrons. Herein, Cu single atoms are confined in a conjugated microporous polymer (CMP) to construct Cu n @CMP photocatalyst for CO 2 reduction to produce C 2 H 4 and CH 4 . By adjusting Cu loading, Cu 0.012 @CMP exhibited a high performance with production yields of 236.81 μmol·g −1 ·h −1 for C 2 H 4 , and 78.2 % selectivity for C 2 H 4 formation. DFT calculations displayed the band structure and confirmed Cu–N together with characterization. The in situ DRIFTS revealed *CH 2 and *C 2 H 4 as key reaction intermediates to form CH 4 and C 2 H 4 , respectively. The synergy effect in Cu single-atoms and CMP contributed greatly to C–C coupling and interfacial charge transfer, thus achieving excellent activity for conversion of CO 2 to C 1 /C 2 . This work highlights the potential for constructing Cu single atoms on CMP to produce highly selective C 2 H 4 .
研究领域:
材料科学
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环境科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
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2025
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IF 17.7
Mengyang Xu,Bingqing Chang,Jinze Li,Huiqin Wang,Pengwei Huo
The assembly of different Metal organic framework (MOFs) into hybrid heterostructures has proven to be a promising strategy that can effectively break through the limited regulatory capacity of single metal sites. Here, an S-scheme heterostructure (Fe 3 Ni-MOF) based on homologous ligands (1,4-phthalic acid) of ultra-thin Ni-MOF and Fe-MOF nanoparticles with directional electron transport channels, was developed and used it for photoreduction of CO 2 . Under the S-scheme electric field mechanism, the photogenerated carrier can achieve efficient directional separation through Fe–O–Ni atomic bond, which significantly reduces the energy barrier of the rate-determining step. Results show that the performance of Fe 3 Ni-MOF (63.5 μmol g –1 ) was 20 and 3.2 times higher than that of Ni-MOF and Fe-MOF, respectively, and exhibits excellent CO selectivity (96.4%) and stability. Transmission electron microscopy and atomic force microscopy revealed the two-molecular-layers structure of Ni-MOF and the micro-assembly structure of Fe 3 Ni-MOF, which can shorten the electron transport distance and increase the molecular mass transfer rate. X-ray photoelectron spectroscopy, electron spin resonance and electron density difference calculations reveal that interfacial electric fields and atomic bonds work together to promote directional carrier separation, resulting in the accumulation of holes on Ni-MOF and electrons on Fe-MOF. The Gibbs free energy calculation and in-situ Fourier transformed infrared spectroscopy validate that the micro-assembled S-scheme heterostructures with directional electron transport channels can significantly reduce the activation energy barrier of the reaction. This study not only proves the feasibility of constructing MOFs S-scheme heterostructures using homologous ligands, but also provides a new way to overcome the limitations of monometallic MOFs. This strategy is expected to open up a new avenue to design efficient photocatalysts.
研究领域:
材料科学
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环境科学
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化学
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DOI
高影响因子
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