3D-Printed MOF Monoliths:Fabrication Strategies and Environmental Applications

Metal-organic frameworks(MOFs)have been extensively considered as one of the most promising types of porous and crystalline organic-inorganic materials,thanks to their large specific surface area,high porosity,tailorable structures and compositions,diverse functionalities,and well-controlled pore/size distribution.However,most developed MOFs are in powder forms,which still have some technical challenges,including abrasion,dustiness,low packing densities,clogging,mass/heat transfer limitation,environmental pollution,and mechanical instability during the packing process,that restrict their applicability in industrial applications.Therefore,in recent years,attention has focused on techniques to convert MOF powders into macroscopic materials like beads,membranes,monoliths,gel/sponges,and nanofibers to overcome these challenges.Three-dimensional(3D)printing technology has achieved much interest because it can produce many high-resolution macroscopic frameworks with complex shapes and geometries from digital models.Therefore,this review summarizes the combination of different 3D printing strategies with MOFs and MOF-based materials for fabricating 3D-printed MOF monoliths and their environmental applications,emphasizing water treatment and gas adsorption/separation applications.Herein,the various strategies for the fabrication of 3D-printed MOF monoliths,such as direct ink writing,seed-assisted in-situ growth,coordination replication from solid precursors,matrix incorporation,selective laser sintering,and digital light processing,are described with the relevant examples.Finally,future directions and challenges of 3D-printed MOF monoliths are also presented to better plan future trajectories in the shaping of MOF materials with improved control over the structure,composition,and textural properties of 3D-printed MOF monoliths.

Hybrid Strategy of Partitioned and Monolithic Methods for Solving Strongly Coupled Analysis of Inverse and Direct Piezoelectric and Circuit Coupling

The inverse and direct piezoelectric and circuit coupling are widely observed in advanced electro-mechanical systems such as piezoelectric energy harvesters.Existing strongly coupled analysis methods based on direct numerical modeling for this phenomenon can be classified into partitioned or monolithic formulations.Each formulation has its advantages and disadvantages,and the choice depends on the characteristics of each coupled problem.This study proposes a new option:a coupled analysis strategy that combines the best features of the existing formulations,namely,the hybrid partitioned-monolithic method.The analysis of inverse piezoelectricity and the monolithic analysis of direct piezoelectric and circuit interaction are strongly coupled using a partitioned iterative hierarchical algorithm.In a typical benchmark problem of a piezoelectric energy harvester,this research compares the results from the proposed method to those from the conventional strongly coupled partitioned iterative method,discussing the accuracy,stability,and computational cost.The proposed hybrid concept is effective for coupled multi-physics problems,including various coupling conditions.

Electrochemically Deposited CZTSSe Thin Films for Monolithic Perovskite Tandem Solar Cells with Efficiencies Over 17%

In spite of the high potential economic feasibility of the tandem solar cells consisting of the halide perovskite and the kesterite Cu2ZnSn(S,Se)4(CZTSSe),they have rarely been demonstrated due to the difficulty in implementing solution-processed perovskite top cell on the rough surface of the bottom cells.Here,we firstly demonstrate an efficient monolithic two-terminal perovskite/CZTSSe tandem solar cell by significantly reducing the surface roughness of the electrochemically deposited CZTSSe bottom cell.The surface roughness(R_(rms))of the CZTSSe thin film could be reduced from 424 to 86 nm by using the potentiostatic mode rather than using the conventional galvanostatic mode,which can be further reduced to 22 nm after the subsequent ion-milling process.The perovskite top cell with a bandgap of 1.65 eV could be prepared using a solution process on the flattened CZTSSe bottom cell,resulting in the efficient perovskite/CZTSSe tandem solar cells.After the current matching between two subcells involving the thickness control of the perovskite layer,the best performing tandem device exhibited a high conversion efficiency of 17.5%without the hysteresis effect.

A 256 Gb/s electronic−photonic monolithically integrated transceiver in 45 nm CMOS

With the explosive development of artificial intelligence(AI),machine learning(ML),and high-performance comput-ing(HPC),the ever-growing data movement is asking for high density interconnects with higher bandwidth(BW),lower power and lower latency[1−3].The optical I/O leverages silicon photonic(SiPh)technology to enable high-density large-scale integrated photonics.

Surface-functionalized hole-selective monolayer for high efficiency single-junction wide-bandgap and monolithic tandem perovskite solar cells

Carbazole moiety-based 2PACz([2-(9H-carbazol-9-yl)ethyl]phosphonic acid)self-assembled monolayers(SAMs)are excellent hole-selective contact(HSC)materials with abilities to excel the charge-transferdynamics of perovskite solar cells(PSCs).Herein,we report a facile but powerful method to functionalize the surface of 2PACz-SAM,by which reproducible,highly stable,high-efficiency wide-bandgap PSCs can be obtained.The 2PACz surface treatment with various donor number solvents improves assembly of 2PACz-SAM and leave residual surface-bound solvent molecules on 2PACz-SAM,which increases perovskite grain size,retards halide segregation,and accelerates hole extraction.The surface functionalization achieves a high power conversion efficiency(PCE)of 17.62%for a single-junction wide-bandgap(~1.77 e V)PSC.We also demonstrate a monolithic all-perovskite tandem solar cell using surfaceengineered HSC,showing high PCE of 24.66%with large open-circuit voltage of 2.008 V and high fillfactor of 81.45%.Our results suggest this simple approach can further improve the tandem device,when coupled with a high-performance narrow-bandgap sub-cell.

A monolithic integrated medium wave Mercury Cadmium Telluride polarimetric focal plane array

A medium wave(MW)640×512(25μm)Mercury Cadmium Telluride(HgCdTe)polarimetric focal plane array(FPA)was demonstrated.The micro-polarizer array(MPA)has been carefully designed in terms of line grating structure optimization and crosstalk suppression.A monolithic fabrication process with low damage was explored,which was verified to be compatible well with HgCdTe devices.After monolithic integration of MPA,NETD<9.5 mK was still maintained.Furthermore,to figure out the underlying mechanism that dominat⁃ed the extinction ratio(ER),specialized MPA layouts were designed,and the crosstalk was experimentally vali⁃dated as the major source that impacted ER.By expanding opaque regions at pixel edges to 4μm,crosstalk rates from adjacent pixels could be effectively reduced to approximately 2%,and promising ERs ranging from 17.32 to 27.41 were implemented.

Monolithic Convex Limiting for Legendre-Gauss-Lobatto Discontinuous Galerkin Spectral-Element Methods

We extend the monolithic convex limiting(MCL)methodology to nodal discontinuous Galerkin spectral-element methods(DGSEMS).The use of Legendre-Gauss-Lobatto(LGL)quadrature endows collocated DGSEM space discretizations of nonlinear hyperbolic problems with properties that greatly simplify the design of invariant domain-preserving high-resolution schemes.Compared to many other continuous and discontinuous Galerkin method variants,a particular advantage of the LGL spectral operator is the availability of a natural decomposition into a compatible subcellflux discretization.Representing a highorder spatial semi-discretization in terms of intermediate states,we performflux limiting in a manner that keeps these states and the results of Runge-Kutta stages in convex invariant domains.In addition,local bounds may be imposed on scalar quantities of interest.In contrast to limiting approaches based on predictor-corrector algorithms,our MCL procedure for LGL-DGSEM yields nonlinearflux approximations that are independent of the time-step size and can be further modified to enforce entropy stability.To demonstrate the robustness of MCL/DGSEM schemes for the compressible Euler equations,we run simulations for challenging setups featuring strong shocks,steep density gradients,and vortex dominatedflows.

Direct field-to-pattern monolithic design of holographic metasurface via residual encoderdecoder convolutional neural network

Complex-amplitude holographic metasurfaces(CAHMs)with the flexibility in modulating phase and amplitude profiles have been used to manipulate the propagation of wavefront with an unprecedented level,leading to higher image-reconstruction quality compared with their natural counterparts.However,prevailing design methods of CAHMs are based on Huygens-Fresnel theory,meta-atom optimization,numerical simulation and experimental verification,which results in a consumption of computing resources.Here,we applied residual encoder-decoder convolutional neural network to directly map the electric field distributions and input images for monolithic metasurface design.A pretrained network is firstly trained by the electric field distributions calculated by diffraction theory,which is subsequently migrated as transfer learning framework to map the simulated electric field distributions and input images.The training results show that the normalized mean pixel error is about 3%on dataset.As verification,the metasurface prototypes are fabricated,simulated and measured.The reconstructed electric field of reverse-engineered metasurface exhibits high similarity to the target electric field,which demonstrates the effectiveness of our design.Encouragingly,this work provides a monolithic field-to-pattern design method for CAHMs,which paves a new route for the direct reconstruction of metasurfaces.

High surface area biocarbon monoliths for methane storage

New energy sources that reduce the volume of harmful gases such as SO_(x)and NO_(x)released into the atmosphere are in constant development.Natural gas,primarily made up of methane,is being widely used as one reliable energy source for heating and electricity generation due to its high combustion value.Currently,natural gas accounts for a large portion of electricity generation and chemical feedstock in manufacturing plastics and other commercially important organic chemicals.In the near future,natural gas will be widely used as a fuel for vehicles.Therefore,a practical storage device for its storage and transportation is very beneficial to the deployment of natural gas as an energy source for new technologies.In this tutorial review,biomaterials-based carbon monoliths(CMs),one kind of carbonaceous material,was reviewed as an adsorbent for natural gas(methane)adsorption and storage.

A benzenesulfonic acid-modified organic polymer monolithic column with reversed-phase/hydrophilic bifunctional selectivity for capillary electrochromatography

Here,a styrene-based polymer monolithic column poly(VBS-co-TAT-co-AHM)with reversed-phase/hydrophilic interaction liquid chromatography(RPLC/HILIC)bifunctional separation mode was success-fully prepared for capillary electrochromatography by the in situ polymerization of sodium p-styrene sulfonate(VBS)with cross-linkers 3-(acryloyloxy)-2-hydroxypropyl methacrylate(AHM)and 1,3,5-triacryloylhexahydro-1,3,5-triazine(TAT).The preparation conditions of the monolith were optimized.The morphology and formation of the poly(VBS-co-TAT-co-AHM)monolith were confirmed by scanning electron microscopy(SEM)and Fourier transform infrared spectroscopy(FT-IR).The separation perfor-mances of the monolith were evaluated systematically.It should be noted that the incorporation of VBS functional monomer can provideπ-πinteractions,hydrophilic interactions,and ion-exchange in-teractions.Hence,the prepared poly(VBS-co-TAT-co-AHM)monolith can achieve efficient separation of thiourea compounds,benzene series,phenol compounds,aniline compounds and sulfonamides in RPLC or HILIC separation mode.The largest theoretical plate number for N,N0-dimethylthiourea reached 1.7×10^(5)plates/m.In addition,the poly(VBS-co-TAT-co-AHM)monolithic column showed excellent reproducibility and stability.This novel monolithic column has great application value and potential in capillary electrochromatography(CEC).

Efficiency-loss analysis of monolithic perovskite/silicon tandem solar cells by identifying the patterns of a dual two-diode model’s current-voltage curves

In this work,we developed a simple and direct circuit model with a dual two-diode model that can be solved by a SPICE numerical simulation to comprehensively describe the monolithic perovskite/crystalline silicon(PVS/c-Si)tandem solar cells.We are able to reveal the effects of different efficiency-loss mechanisms based on the illuminated current density-voltage(J-V),semi-log dark J-V,and local ideality factor(m-V)curves.The effects of the individual efficiency-loss mechanism on the tandem cell’s efficiency are discussed,including the exp(V/VT)and exp(V/2VT)recombination,the whole cell’s and subcell’s shunts,and the Ohmic-contact or Schottky-contact of the intermediate junction.We can also fit a practical J-V curve and find a specific group of parameters by the trial-and-error method.Although the fitted parameters are not a unique solution,they are valuable clues for identifying the efficiency loss with the aid of the cell’s structure and experimental processes.This method can also serve as an open platform for analyzing other tandem solar cells by substituting the corresponding circuit models.In summary,we developed a simple and effective methodology to diagnose the efficiency-loss source of a monolithic PVS/c-Si tandem cell,which is helpful to researchers who wish to adopt the proper approaches to improve their solar cells.

Replacement of Unesthetic Posterior Metal Crowns with Monolithic Zirconia Crowns: A Case Report

Advances in metal-free materials and the popularization of Computer-Aided Design and Manufacturing (CAD/CAM) have led to the wide clinical use of all-ceramic crowns for esthetic restorations. A 72-year-old woman presented to our hospital with unesthetic restorations on the right upper and lower posterior teeth. Intraoral examination revealed poorly fitting metal crown margins. Defective prostheses were removed, and provisional restorations were provided to stabilize the mandibular position. Optical impressions and the maxillomandibular relationship were recorded using an intraoral scanner, and monolithic zirconia crowns were fabricated using CAD/CAM technology for complete veneer crown restorative treatment. Occlusal examination revealed an improvement in occlusal force distribution at initial examination (right side: 33.5%, left side: 66.5%) after placement of the zirconia crowns (right side: 54.9%, left side: 45.1%). Occlusal force and occlusal force distribution area also showed an increasing trend. The Oral Health Impact Profile short form (OHIP-14) score decreased from 7 points at initial examination to 0 points after prosthodontic treatment. Appropriate diagnosis and treatment planning contributed to the increased occlusal force and balanced occlusal force distribution. Therefore, the present case indicates the potential of monolithic zirconia crowns to achieve both esthetic and stable functional outcomes.

A Monolithic Integrated CMOS Thermal Vacuum Sensor

The monolithic integrated micro sensor is an important direction in the fields of integrated circuits and micro sensors. In this paper,a monolithic thermal vacuum sensor based on a micro-hotplate （MHP） and operating under constant bias voltage conditions was designed. A new monolithic integrating mode was proposed,in which the dielectric and passiva- tion layers in standard CMOS processes were used as sensor structure layers,gate polysilicon as the sacrificial layer,and the second polysilicon layer as the sensor heating resistor. Then, the fabricating processes were designed and the monolithic thermal vacuum sensor was fabricated with a 0. 6μm mixed signal CMOS process followed by sacrificial layer etching technology. The measurement results show that the fabricated monolithic vacuum sensor can measure the pressure range of 2- 10^5 Pa and the output voltage is adjustable.

RELEASE KINETICS OF MONOLITHIC MATRIX COATED WITH OUTER MEMBRANE SYSTEM

The reservoir-monolithic type of the controlled release systems is investigated currently,however,the existing kinetic model could not describe the release process well because the release kinetics is rather complicated.In this paper,a simplified release kinetic model for diffusion-controlled monolithic matrix coated with outer membrane systems is proposed and verified by the experimental data of mercaptopurinum release experiment.It shows that the model can well describe the release mechanism (the relative error is under 3%) when drug loading (C d) is above its solubility limit (C s).At the same time,the release characteristics of special cases (D mD f and D mD f) are discussed theoretically.When D mD f the release rate becomes constant,namely,zero order release,and the release rate is independent of the drug membrane.This result provides the theoretical basis for the system of zero order release as well as how to control the release rate and the amount of drug release.When D mD f,the release rate is dependent on the drug release coefficient in the monolithic matrix,solubility and drug loading but independent of the process in the outer membrane,and it is similar to monolithic matrix type.

Strongly Gain Coupled DFB Laser Monolithically Integrated with a Self Alignment Spot Size Converter

A new type strongly gain coupled (GC) DFB laser and a new type self alignment spot size converter (SA SSC) are proposed and successfully fabricated.The strongly GC DFB laser is monolithically integrated with the SA SSC with three step epitaxies.A high single mode yield and large side mode suppression ratio is obtained from the strongly GC DFB laser.A near circle far field pattern is obtained by using the SA SSC.

Monolithic特征标的零点与可解群的导长

给出了分别满足条件(M1)G的monolithic特征标没有公共的零点;(M2)G的非线性不可约monolithic特征标中最多有两个有公共的零点,的有限群的一个导长的上界.

Co-Design of Monolithically Integrated Photo-Detector and Optical-Receiver

A behavioral model of the photodiode is presented.The model describes the relationship between photocurrent and incident optical power,and it also illustrates the impact of the reverse bias to the variation of the junction capacitance.According to this model,the photodiode and a CMOS receiver circuit are simulated and designed simultaneously under a universal circuit simulation environment.

MATHEMATICAL ANALYSIS OF DRUG RELEASE FROM A MONOLITHIC MATRIX WITH AN INITIALLY LINEAR CONCENTRATION DISTRIBUTION

Based on the principle of chemical engineering in the multisubject field—drug delivery, the release kinetics of the slab monolithic matrix with an initially linear concentration distribution is studied in this paper. It can be used to describe the later stage when drug loading is above its solubility limit. A comprehensive model is proposed and the generalized solutions are acquired by Laplace transformation, from which a special case, i.e. a perfect sink has been deduced. According to the derived equations, the concentration profiles in the matrix has been computed and illustrated and the effect of volume of extraction medium on release has been investigated.

Monolithically Integrated Optoelectronic Receivers Implemented in 0.25μm MS/RF CMOS

A monolithically integrated optoelectronic receiver is presented. A silicon-based photo-diode and receiver circuits are integrated on identical substrates in order to eliminate the parasitics induced by hybrid packaging. Implemented in the present deep sub-micron MS/RF （mixed signal, radio frequency） CMOS,this monolithically OEIC takes advantage of several new features to improve the performance of the photo-diode and eventually the whole OEIC.

2.5 Gbit/s monolithic ICs for optical fiber transmitter and receiver in 0.35 μm CMOS process

2.5 Gbit/s monolithic integrated circuits （ICs） for optical fiber transmitter and receiver in 0.35 μm CMOS （complementary metal-oxide-semiconductor transistor） process are presented. The transmitter, which includes a 4： 1 multiplexer and a laser diode driver （LDD）, has four 622 Mbit/s random signals as its inputs and gets a 2.5 Gbit/s driving signal as its output; the receiver detects a 2.5 Gbit/s random signal and gets four 622 Mbit/s signals at the output. The main circuits include a trans-impedance amplifier （TIA）, a limiting amplifier, a clock and data recovery （CDR） unit, and a 1： 4 demultiplexer （DEMUX）. Test results prove the logic functions of the transmitter to be right, and the 10% to 90% rise and fall times of transmitter＇s output data eye diagram are 211.1 ps and 200 ps, respectively. The sensitivity of the receiver is measured to be better than 20 mV. The root mean square jitter of the DEMUX＇s output data is 15.6 ps and that of the clock after 1： 4 frequency dividing is 1.9 ps. Two chips are both applicable to 2.5 Gbit/s optical fiber communication systems.