INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Tianyue Wang,Jia Liu,Bining Tian,Lulu Yan,Zhanfeng Li,Yue Tian
Engineering surface reaction kinetics plays a vital role in promoting CO2 photoreduction reaction (CO2 PRR) efficiency but remains formidably challenging. Here, we demonstrate that the regulation of the surface oxidation state is an effective strategy for the unification of the adsorption sites and reactive centers, which significantly improves the reaction kinetics and CO2 PRR efficiency. Taking advantage of the concept, we further propose p–p orbital hybridization between P atoms and the adjacent O atoms in BiVO4 at the interface constructed in the O-RP/BiVO4 Z-scheme heterostructure to create the oxidation state of RP. Theoretical calculations and spectral characterizations reveal that the interfacial atomic orbital hybridization lowers the CO2 activation energy barrier through the stabilization of the COOH* intermediate and facilitates the charge separation and transfer. Consequently, the optimized photocatalyst exhibits an excellent performance for sacrificial reagent-free CO2 PRR, with a production rate of 208 and 26.2 μmol g–1 h–1 for CO and CH4, respectively, ca. 21-fold higher than that of pristine RP and topping most of the hybrid photocatalysts with a noble metal as cocatalysts. This work provides critical insight for the design of high-efficiency photocatalysts for CO2 PRR.
研究领域:
材料科学
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环境科学
·
光催化
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2025
·
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
·
化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2020
·
IF 8.758
Pan Li,Haifeng Hu,Gan Luo,Shuang Zhu,Lingju Guo,Peng Qu,Qi Shen,Tao He
Crystal facet engineering provides a promising approach to tailor the performance of catalysts because of the close relationship between the photocatalytic activity and the surface atomic and electronic structures. An in-depth understanding mechanism of crystal facet-dependent CO2 photoreduction is still an open question. Herein, two different types of porous ZnO nanocatalysts are used as model photocatalysts for the investigation, which are, respectively, with exposed {110} and {001} facets. The porous ZnO with an exposed {110} facet exhibits superior photocatalytic activity to the one with the {001} facet. Various influencing factors have been thoroughly studied both theoretically and/or experimentally, including light harvesting (i.e., band gap), reduction capability (potential of conduction band), crystallinity, CO2 adsorption ability, CO2 activation, and charge separation. The major influencing factors are eventually figured out based on the experimental and calculation results. The product selectivity and the influence of the hole scavenger can be explained too. Our work may pave a way for directing the future rational design of efficient photocatalysts for CO2 reduction.
研究领域:
材料科学
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环境科学
·
化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Yang Li,Qiao Yin,Yingshan Zeng,Zhi Liu
The core of realizing the effective CO 2 conversion by solar energy is to develop a stable photocatalyst with high CO 2 adsorption capacity and high charge separation efficiency. In this work, a hollow spherical Z-scheme SnS 2 /g-C 3 N 4 /C (SCC) photocatalyst is successfully constructed by a morphology-inherited strategy. Biomass mabospores are utilized as both the precursor for formation of hollow spherical structure and carbon source, and the g-C 3 N 4 and SnS 2 nanosheets tightly anchor on the surface of mabospores-derived carbon spheres. The Z-scheme SCC heterostructure exhibits 5.5 times activity enhancement on CO 2 photoreduction to CO with a high evolution rate up to 40.86 μmol∙g −1 ∙h −1 . Examined by various photoelectrochemical analysis, the boosted photocatalytic activity originates mainly from the construction of hollow spherical Z-scheme heterojunction, providing the more preferable basic sites for CO 2 adsorption, promoting the separation efficiency of electron-hole pairs, as well as increasing the reductionability of electrons in conduction band of g-C 3 N 4 . The formed internal electric fields between the g-C 3 N 4 and SnS 2 can also further reinforce the spatial separation of photogenerated charge carriers. Theoretical calculations further verify that the SCC Z-scheme heterostructure can effectively decrease the energy barriers of formed intermediates, especially the crucial COOH*, and thus leading to the facile conversion of CO 2 -to-CO. This work induces a new strategy to construct g-C 3 N 4 -based Z-scheme heterojunction assisted by versatile biomasses with optimized structure and enhanced photoelectrochemical merits for efficient CO 2 conversion into chemical fuels.
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
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2018
·
IF 11.698
Yanan Liu,Chenglin Miao,Pengfei Yang,Yufei He,Junting Feng,Dianqing Li
The ultrathin TiO 2 nanosheets (TiO 2 -U) with abundant defects were successfully fabricated as substrates to support well-dispersed Pt nanoparticles with low metal loading by photochemical route (P), with impregnated Pt/TiO 2 -U, Pt/TiO 2 -bulk and photoreduced Pt/TiO 2 -bulk as control samples, to focus on studying the inductive effect of oxygen vacancy-rich ultrathin TiO 2 on highly dispersed Pt nanoparticles, and their synergetic promotional effect for CO 2 photoreduction. As expected, P-Pt/TiO 2 -U exhibited excellent photocatalytic efficiency for the selective conversion of CO 2 into CH 4 and CO. The ultrathin TiO 2 nanosheets with a large number of low coordinative sites and ultralarge surface area promoted the rate of electron-transfer. The ultrafine Pt nanoparticles induced by photochemical strategy facilitated the efficient separation of electron–hole pairs. Furthermore, the synergy of metal and support improved the adsorption ability of CO 2 . These three factors were considered to drive jointly the enhancement of catalytic performance in this system. This work offers deep insights for the design of highly efficient catalysts with coordinatively unsaturated sites for CO 2 photoconversion in the presence of H 2 O.
研究领域:
材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2023
·Vol. 33
·期 28
·2301729
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IF 19
Youyu Duan,Yang Wang,Weixuan Zhang,Jiangwei Zhang,Chaogang Ban,Danmei Yu,Kai Zhou,Jinjing Tang,Xu Zhang,Xiaodong Han,Liyong Gan,Xiaoping Tao,Xiaoyuan Zhou
Photocatalytic conversion of CO 2 into fuels using pure water as the proton source is of immense potential in simultaneously addressing the climate-change crisis and realizing a carbon-neutral economy. Single-atom photocatalysts with tunable local atomic configurations and unique electronic properties have exhibited outstanding catalytic performance in the past decade. However, given their single-site features they are usually only amenable to activations involving single molecules. For CO 2 photoreduction entailing complex activation and dissociation process, designing multiple active sites on a photocatalyst for both CO 2 reduction and H 2 O dissociation simultaneously is still a daunting challenge. Herein, it is precisely construct Cu single-atom centers and two-coordinated N vacancies as dual active sites on CN (Cu 1 /N 2C V-CN). Experimental and theoretical results show that Cu single-atom centers promote CO 2 chemisorption and activation via accumulating photogenerated electrons, and the N 2C V sites enhance the dissociation of H 2 O, thereby facilitating the conversion from COO* to COOH*. Benefiting from the dual-functional sites, the Cu 1 /N 2C V-CN exhibits a high selectivity (98.50%) and decent CO production rate of 11.12 µmol g −1 h −1 . An ingenious atomic-level design provides a platform for precisely integrating the modified catalyst with the deterministic identification of the electronic property during CO 2 photoreduction process.
研究领域:
催化化学
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环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
·
2024
·Vol. 14
·期 10
·659
·
IF 3.8
Dandan Wang,Xiaofei Yan,Xinsheng Zhu,Ying Liu,Laihong Zhang,Yaqiu Lu,Jie Li,Dingming Xue
Photoreduction of CO2into the chemical feedstocks of fuels provides a green way to help solve both the energy crisis and carbon emission issues. Nevertheless, undesirable charge separation and migration, as well as rapid reverse charge recombination results in the unsatisfactory photocatalytic activity of most conjugated microporous polymers (CMPs). Herein, a pair of donor–acceptor (D-A) CMPs for CO2photoconversion was developed through position isomerism by altering linkage sites. The results show that Py-D27F with 2,7-site linkage exhibits a completely conjugated structure and a large molecular dipole moment, thus significantly accelerating charge separation and transfer. As a result, Py-D27F achieves a higher yield of 320.9 μmol g−1h−1for CO2-to-CO photoreduction (without the addition of any photosensitizers and precious metals), which is about three-fold greater than that of Py-D36F (3,6-site linkage). This study provides a valuable idea for exploring outstanding CMP photocatalysts for the efficient processing of photocatalysis.
研究领域:
材料科学
·
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
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2019
·
IF 14.229
Ruiyang Zhang,Penghui Li,Fang Wang,Liqun Ye,Abhijeet Gaur,Zeai Huang,Ziyan Zhao,Yang Bai,Ying Zhou
Atomically dispersed atom catalysts with atomically distributed active metal centers have attracted great attention owing to the maximum atom efficiency and excellent selectivity. Herein, for the first time, we found atomically dispersed Mo atoms can be formed on g-C 3 N 4 , and induce its amorphous transformation. This amorphous transformation leads to the formation of strong band tails with remarkably enhancing the absorbance edge of Mo-C 3 N 4 up to 750 nm, resulting in almost whole visible-light range absorption. The formation of new Mo-C and Mo-N bonds due to strong interfacial interaction between atomically dispersed Mo atoms and g-C 3 N 4 provide new electron and hole transport pathways to accelerate the separation of charge carriers. As a result, amorphous Mo/C 3 N 4 (a-Mo/C 3 N 4 ) reveals excellent photoreduction of CO 2 , yielding CO and H 2 productions of 18 and 37 μmol g −1 h −1 under visible-light illumination (λ > 420 nm), which manifest a remarkable 10.6- and 4-folds enhancement of that over crystalline g-C 3 N 4 . This finding provides a conceptually different approach to fabricate high-efficient photocatalyst through the strong interfacial interaction between atomically dispersed metal atoms and host.
研究领域:
材料科学
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催化化学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Jing Lei,Wei Bi,Mitang Wang,Hao Jiang,Yanjie Hu,Chunzhong Li
How to achieve controllable preparation of heterostructure and in-situ optimize the interface and internal electron transfer by a fast and economic synthesis method has become a big challenge in the practical application of photocatalysis. Herein, an island-shaped SrTiO 3 (STO) perovskite nanodots and TiO 2 (T) compounded S-scheme SrTiO 3 /TiO 2 (ST) heterostructure was successfully developed. During the millisecond reaction process, the decomposed Sr 2+ penetrated into the TiO 2 lattice causing the lattice expansion and inducing local atomic rearrangements, resulting in the generation of STO phase. Owing to the synergy of the efficient electron transport at the perovskite nanodots interface and the stronger reduction capacity, the performance of the optimized ST1 sample is greatly improved to 86.90 μmol g −1 for CO 2 -to-CO and 21.31 μmol g −1 for CO 2 -to-CH 4 . The utilization of electrons reached up to 119.74 μmol g −1 h −1 , which was 3.13 times higher than that of T. Detailed characterizations and density functional theory (DFT) calculations proof that the formation of intermediates HCOO − and CO 3 2− is the key to the performance improvement critically. Overall, this work originally reports a feasible strategy for flame synthesis of S-scheme heterostructure photocatalyst.
研究领域:
光催化
·
材料科学
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Inorganic Chemistry Frontiers
·
2025
·
IF 6.4
Lu-Wen Qiu,Wen-Ni Zhang,Lin-Ying Wang,Hao Li,Tian-Kuan Zhang,Mi-Xin Lin,Su-Qin Ci,Jian Lü
In this work, morphological control with a series of sulfur-vacancy-rich CdS photocatalysts has been achieved toward the optimization of their performances in CO2 photoreduction. Results show that sulfur-vacancy-rich CdS nano-platelets (p-CdS-Vs) exhibit the highest CO2 photoreduction activity with a CO yield of 4058.5 μmol h−1 g−1, which is 10 and 6 times those of sulfur-vacancy-rich CdS nanowires (w-CdS-Vs, 372.8 μmol h−1 g−1) and nanorods (r-CdS-Vs, 638.7 μmol h−1 g−1), respectively, amongst the highest numbers for CdS-based photocatalysts reported hitherto. The superior CO2 photoreduction performance of p-CdS-Vs is attributable to its high efficiency of electron transport and suppressed recombination of photogenerated charge carriers. A mechanistic study indicates the critical role of surface sulfur vacancies that provide a microenvironment to trap unpaired electrons for the separation of photogenerated carriers so that the photocatalytic efficiency of CO2-to-CO reduction is largely improved in this current system.
研究领域:
材料科学
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环境科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
·
2021
·Vol. 23
·期 8
·4690-4699
·
IF 3.676
Zhengyan Zhao,Wei Liu,Yantao Shi,Heming Zhang,Xuedan Song,Wenzhe Shang,Ce Hao
We report a combination of experimental and computational mechanistic studies for the photoreduction of CO2 to CO with water, catalyzed by single-atom Fe supported on graphitic carbon nitride (g-C3N4). Density functional theory (DFT) and time-dependent DFT (TDDFT) methods were utilized to explore the behavior of single-atom Fe in g-C3N4, which is of vital importance to the understanding of the CO2 reduction reaction (CO2RR) mechanism. The calculation results reveal that the rate-limiting step of the hydrogen-bonded complex in the absence of Fe atoms is the cleavage of C–O bonds in COOH radicals during the whole CO2RR, which includes the photophysical and photochemical processes. The presence of Fe atoms not only activated CO2 in the ground state and increased the rate constant of the limiting step in the photophysical process, but also functioned as the catalytic active center, lowering the reaction barrier of the C–O bond cleavage in COOH˙ in the photochemical process and resulting in improved photocatalytic activity. In addition, DFT calculations further demonstrated that the electron and proton transfer involved in the photophysical and photochemical processes is closely related to and induced by the hydrogen bonds in the excited state.
研究领域:
材料科学
·
催化化学
·
环境科学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2020
·
IF 10.652
Shikang Yin,Linlin Sun,Yaju Zhou,Xin Li,Jinze Li,Xianghai Song,Pengwei Huo,Huiqin Wang,Yongsheng Yan
The use of semiconductor photocatalytic reduction technology has higher efficiency and lower energy consumption for CO 2 reduction, but its existence of some mismatched energy band positions and relatively slow charge-hole separation greatly limits its practical application. In this paper, a SnS 2 /Au/g-C 3 N 4 embedded structure model with carbon and nitrogen hybridization is proposed to gain an in-depth understanding of the role of hybridization and precious metal modification in photocatalysis. Carriers were investigated from the perspective of kinetics through photocurrent, LSV curve, and FL spectroscopy. After modification of Au nanoparticles, the photo-excited electrons showed a slower decay process, indicating that the separation of carriers was enhanced, which was further confirmed by impedance and PL spectroscopy. SEM, AFM and TEM analysis confirmed that the 2D face-to-face SnS 2 /Au/g-C 3 N 4 embedded structure was successfully prepared and the Au nanoparticles were evenly distributed. Au nanoparticles not only act as a bridge for electron transport in 2D semiconductor materials to accelerate electron transport, but generate more excited electrons by themselves under the radiation of sunlight, which effectively improves the separation efficiency of electron-hole pairs and enhances the photocatalyst activity. DFT calculations show that the Z-type mechanism and the intercalated energy level of the SnS 2 /Au/g-C 3 N 4 embedded structure expand the light absorption and improve the carrier separation efficiency. As expected, the photocatalyst activity with CO and CH 4 the evolution rate of up 93.81 µmol·g −1 ·h −1 and 74.98 µmol·g −1 ·h −1 under visible light irradiation, respectively, while the photocatalytic activity is negligible loss after 30 h photoreduction. This work reveals the role of embedded structure and precious metal modification in the separation and transmission of electron-hole, opening up new perspective for achieving high-efficiency solar CO 2 reduction performance.
研究领域:
材料科学
·
环境科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）